Polyurethane products

ABSTRACT

POLYURETHANE PRODUCTS ARE OBTAINED BY REACTING ORGANIC POLYISOCYANATES WHICH ARE CHARACTERIZED BY A COMMON STRUCTURAL UNIT, WITH ACTIVE HYDROGEN CONTAINING COMPOUNDS AS DETERMINED ACCORDING TO THE ZEREWITINOFF METHOD. THESE PRODUCTS HAVE A HIGH DEGREE OF UTILITY IN FIELDS SUCH AS CAST AND THERMOPLASTIC POLYURETHANES, REINFORCED PLASTICS, ELASTIC FIBERS AND FILMS, COATINGS, URETHANE FOAMS ESPECIALLY RIGID URETHANE FOAM PRODUCTS, ETC.

United States Patent Ofice 3,677,983 Patented July 18, 1972 U.S. Cl. 260-25 AT Claim ABSTRACT OF THE DISCLOSURE Polyurethane products are obtained by reacting organic polyisocyanates which are characterized by a common structural unit, with active hydrogen containing compounds as determined according to the Zerewitinoif method. These products have a high degree of utility in fields such as cast and thermoplastic polyurethanes, reinforced plastics, elastic fibers and films, coatings, urethane foams especially rigid urethane foam products, etc.

This application is a divisional application of application Ser. No. 478,400 entitled Novel Cyclic Unsaturated Isocyanates and Products There-from, by T. K. Brotherton, J. W. Lynn, and R. J. Knopf, filed Aug. 9, 1965, now U.S. Pat. No. 3,553,249, which in turn is a continuation-in-part of application Ser. No. 256,495 entitled Novel Ester Isocy-anates and Process for Preparation, by T. K. Brotherton, J. W. Lynn, and R. J. Knopf, filed Jan. 25, 1963, now U.S. Pat. No. 3,275,679 and application Ser. No. 265,367 entitled Novel Halogenated Isocyanates and Process for Preparation, by T. K. Brotherton, J. W. Lynn, and R. I. Knopf, filed Mar. 15, 1963, now abandoned, all of the aforesaid applications being assigned to the same assignee as the instant application.

This invention relates to novel isocyanate compositions and to the processes for preparing the same. In one aspect, the invention relates to novel polymers of isocyanate compositions which polymers contain a plurality of ethylene bonds, i.e., C=C In another aspect, the invention relates to novel polymers of several of the above-said isocyanate compositions, said polymers containing a plurality of pendant isocyanato groups, i.e., -NCO. In a further aspect, the invention relates to novel compositions which result from the reaction of novel isocyanates with active hydrogen compounds. In various aspects, the invention relates to the preparation of novel cast resins, thermoplastic resins, millable gum stocks and the cured products therefrom, prepolymers, elastomers, elastic and relatively non-elastic fibers, urethane foams, including flame-retardant foams, adhesives, coatings, reinforced plastics, and the like.

The novel isocyanate compounds which are contemplated can be represented by Formula I infra.

wherein X represents hydrogen; halogen, e.g., chlorine, bromine, iodine, etc.; and alkoxy Which preferably contains from 1 to 6 carbon atoms; wherein X represents hydrogen; halogen, e.g., chlorine, bromine, iodine, etc.; and alkoxy which preferably contains from 1 to 6 carbon atoms; wherein y is an integer having a value of zero or one; wherein A represents oxygen or carbon; wherein G represents one of the following structures:

with the proviso that (1) all the X variables (and preferably the X plus X variables) are halogen, especially chlorine, when G represents one of the structural units designated as (a) through (f) inclusive above, and (2) when A is oxygen, y is zero, and when A is carbon, y is one. Thus A can be the oxy group (-0) or the ii-t) group.

oxycarbonylalkyl, oxycarbonylalkyl, alkylenecarbonyloxyalkyl, and the like.

The R variable in the appropriate structural units above represents hydrogen or a hydrocarbon group which preferably contains from 1 to 24 carbon atoms, and preferably still, from 1 to 12 carbon atoms, such as alkyl, cycloalkyl, aryl, alkaryl, and aralkyl, e.g., methyl, ethyl, propyl, butyl, dodecyl, cyclohexyl, phenyl, benzyl, phenethyl, tolyl, xylyl, and the like.

The R variable in units (i) through (1) above represents a divalent aliphatic radical, especially a divalent aliphatic hydrocarbon radical, for example, alkenylene or alkylene of 2 to 18 carbon atoms, preferably alkenylene or alkylene of 2 to 10 carbon atoms. The variable R represents hydrogen or alkyl which preferably contains from 1 to 6 carbons. The variable a is an integer which has a value of zero or one, whereas the variable b is an integer which has a value of 1 to 3.

The variable In in units (a) through (h) above is an integer which has a value of from 1 to 3, preferably from 1 to 2. The variable n is an integer which has a value of zero or one, with the proviso that when n is zero then m is one.

Various highly useful and attractive subclasses of novel isocyanate compositions which fall Within the metes and bounds of Formula I supra are as follows:

the bis(isocyanatoalkyl) -norbornene-2,3-dicarboxyl ates;

the bis(isocyanatoalkenyl) 5-norbornene-2,3-dicarboxylates;

the bis(isocyanatocycloalkyl) 5-norbornene-2,3-dicarboxylates;

the bis(isocyanatoaryl) 5-norbornene-2,3-dicarb0xylates;

the bis(isocyanatohydrocarbyl) 2,5-norbornadiene-2,3-

dicarboxylates;

the bis(isocyanatoalkyl) 2,5-norbornadiene-2,3-dicarboxylates;

the 2,3-bis(isocyanatohydrocarbyloxycarbonylalkyD-S- norbornenes;

the 2,3-bis(isocyanatoalkoxycarbonylalkyl)-5-norbornenes;

the bis(isocyanatohydrocarbyD-5-norbornene-2,3-dicarboxylates;

the 2,3-bis(isocyanatoalkoxycarbonylalkyl)-2,5-norbornadienes;

the bis(isocyanatohydrocarbyl) 3,6-endo-oxo-4-cyclohexene-l,Z-dicarboxylates;

the bis(isocyanatoalkyl) 3,6-endo-oxo-4-cyclohexene- 1,2-dicarboxylates;

the bis(isocyanatoalkenyl) 3,6-endo-oxo-4-cyclohexene- 1,2-dicarboxylates;

the bis(isocyanatoaryl) 3,6-endo-oxo-4-cyclohexene- 1,2-dicarboxylates;

the bis(isocyanatohydrocarbyl) 3,6-endo-oxo-1,4-cyclohexadiene-1,2-dicarboxylates;

the bis(isocyanatoalkyl) 3,6-endo-oxo-1,4-cyc1ohexadiene-l,2-dicarboxylates;

the bis(isocyanatoalkenyl) 3,6-endo-oxo-l,4-cyclohexadiene-1,2-dicarboxylates;

the bis(isoeyanatoaryl) 3,6-endo-oxo-1,4-cyclohexadiene- 1,2-dicarboxylates;

the hexachlorinated 2-isocyanatoalkyl-S-norbornenes;

the hexachlorinated 2-isocyanatoalkenyl-S-norbornenes;

the hexachlorinated 2-isocyanatocycloalkyl-5-norbornenes;

the hexachlorinated 2-isocyanatocycloalkenyl-S-norbornenes;

the hexachlorinated 2-isocyanatoaryl-S-norbornenes;

the hexachlorinated 2-isocyanatoalkaryl-5-norbornenes;

the hexachlorinated 2-(isocyanatoalkoxyalkyl)-5-n0rbornenes;

the hexachlorinated 2-(isocyanatoaryloxyalkyl)-5-norbornenes;

the hexachlorinated isocyzmatoalnyl 5-norbornene-2- 4 carboxylates; the hexachlorinated isocyanatoaryl 5-norbornene-2- carboxylates;

the hexachlorinated 5-norbornen-2-ylalkyl isocyanatoalkanoates;

the hexachlorinated 2,3-bis(isocyanatoalkyl)-5-norbornenes;

the hexachlorinated 2,3-bis(isocyanatoalkenyl) -5-norbornenes;

the hexachlorinated 2,3-bis(isocyanatocycloalkyl)-5- norbornenes;

the hexachlorinated 2,3-bis(isocyanatoaryl)S-norbornenes;

the hexachlorinated 2,3-bis(isocyanatoalkoxyalkyl)-5- norbornenes;

the hexachlorinated 2,3-bis(isocyanatoaryloxyalkyl)-5- norbornenes;

the hexachlorinated bis(isocyanatoalkyl) 5-norb0rnene- 2,3-dicarboxylates;

the hexachlorinated bis(isocyanatoaryl) 5-norbornene- 2,3-dicarboxylates;

the hexachlorinated S-norbornenyl-Z,3-dialkyl bis(isocyanatoalkanoates the hexachlorinated 2-isocyanatoalkyl-2,5-norbornadienes;

the hexachlorinated 2,3-bis(isocyanatoalkyl)-2,5-norbornadienes;

the hexachlorinated 2,3-bis(isocyanatoalkenyl)-2,5-

norbornadienes;

the hexachlorinated 2,3-bis(isocyanatocycloalkyl)-2,5-

norbornadienes;

the hexachlorinated 2,3-bis (isocyanatocycloalkenyl)- 2,5-norbornadienes;

the hexachlorinated 2,3-bis(isocyanatoaryl)-2,5-

norbornadienes;

the hexachlorinated 2,3-bis(isocyanatoalkaryl)-2,5-

norbornadienes;

the hexachlorinated 2,3-bis (isodyanatoalkoxyalkyl)-2,5-

norbornadienes;

the hexachlorinated 2,3-bis(isocyanatoaryloxyalkyl)- 2,5-norb0rnadienes;

the hexachlorinated bis(isocyanatoalkyl) 2,5-norbornadithe ene-2, 3-dicarboxylates;

the hexachlorinated bis(isocyanatoaryl) 2,5-norbornadiene-2,3-dicarboxylates;

the hexachlorinated 2,5-norbornadienyl-2,3-dialkyl bis- (isocyanatoalkanoates) the hexachlorinated S-norborenyl-Z-alkyl diisocyanatoacylate;

the hexachlorinated 5-norbornenyl-2-alkyl 3,5-diisocyanatobenzoates;

the hexachlorinated norborn-S-en-Z-ylalkyl isocyanates;

the hexachlorinated bis(isocyanatoalkyl) 1,425,8-dimethano-l,2,3,4,5,8,9,10-octahydronaphthalene-2,3- dicarboxylate;

the hexachlorinated octahydro-Z-(isocyanatoalkyl)- 1,4:5,8-dimethanonaphthalene;

and the like.

Specific novel isocyanate compounds which are contemplated include, for example,

1,4,5,6,7,7-hexachloro-5-norbornenyl-Z-methyl 3,5-diisocyanatobenzoate,

8-( 1,4,5,6,7,7-hexachl0ronorborn-S-en-Z-yl)octyl lsocyanate,

4-( 1,4,5 ,6,7,7-hexachloronorborn-S-en-yl(butyl isocyanate,

2- 1,4,5 ,6,7,7-hexachloro-S-norbornenyl)methyl 2,4-diisocyanatophenyl ether,

bis(Z-isocyanatoethyl) 5-norbornene-2,3-dicarboxylate,

bis(2-isocyanato-l-methylethyl) 5-norbomene-2,3-

dicarboxylate,

bis(3-isocyanatopropyl) 5-norbornene-2,3-dicarboxylate,

bis(l8-isocyanatooctadecyl) 5-norbornene-2,3-

dicarboxylate,

2- 3 -isocyanatopropyl -3 4-isocyanatobuten-2-yl 1,4,5,6,7,7-hexachloro-5-norbornene,

2- 7-isocyanatoheptyl -3- 4-isocyanatocyclohexyl) 1,4,5,6,7,7-hexachloro-5-norbornene,

2-(4-isocyanatophenyl) -3- (3 ,5 -diisocyanatophenyl) 1,4,5,6,7,7-hexachloro-S-norbornene,

2- (4-isocyanatophenyl -3 2-is0cyanatoethyl l ,4,5 ,6,7,7-

hexachloro-S-norb ornene,

2-isocyanat0-1,4,5,6,7,7-hexachloro-2,5-norbornadiene,

2-isocyanatomethyl- 1 ,4,5,6,7,7-hexachloro-2,5-

norbornadiene,

2,3-bis (isocyanatomethyl l ,4,5,6,7,7-hexachloro-2,5-

norbornadiene,

2-isocyanatornethyl-1,4,5,6,7,7-heXachloro-2,5-

norbornadiene,

2,3-bis (isocyanatomethyl 1 ,4,5 ,6 ,7,7-hexachlor0-2,5

norbornadiene,

3-isocyanatopropyl 1,4,5,6,7,7-hexachloro-2,5-

norbornadiene-Z-carboxylate,

bis 2-isocyanatoethyl) 1,4,5 ,6,7,7-hexachloro-2,5-

norbornadiene-2,3-dicarboxylate,

2,3-diisocyanato-1,4,5,6,7,7-hexachl0ro-2,5-norbornadiene,

2,3-bis (isocyanatomethyl l ,4,5,6,7,7-hexachl0ro-2,5-

norbornadiene,

2,3-bis(2-isocyanatoethyl)-1,4,5,6,7,7-hexachloro-2,S-

norborn adiene,

2,3-bis(4-isocyanatobutyl)-1,4,5,6,7,7-hexachloro-2,5-

norbornadiene,

2,3-bis(18-isocyanatooctadecyl)-1,4,5,6,7,7-hexach1oro- 2,5 -norbornadiene,

2,3-bis(6,12,18-triisocyanato0ctadecyl)-1,4,5,6,7,7-

hexachloro-2,S-norbornadiene,

2,3-bis(4-isocyanatobuten-2-yl)-1,4,5,6,7,7-hexachloro- 2,5 -norbornadiene,

2,3-bis(12-isocyanatododecen-S-yl)-1,4,5,6,7,7-

hexachloro-2,S-norbornadiene,

2,3-bis(8,10-diisocyanatooctadecen-4-yl)-1,4,5,6,7,7-

hexachloro-2,5-norbornadiene,

2,3-bis (4-isocyanatocyclohexyl) 1 ,4,5,6,7,7-hexachloro- 2,5-norbornadiene,

2,3-bis(2,4,6-triisocyanatocyclohexyl) -1,4,5,6,7,7-

hexachloro-Z,S-norbornadiene,

2,3-bis(4-is0cyanatocyclohexen-Z-yl)-1,4,5,6,7,7-

hexachloro-2,5-norbornadiene,

2,3-bis 3,5 -diisocyanatocyclohexen-Z-yl l ,4,5 ,6,7,7-

hexachloro-2,5-norbornadiene,

2,3-bis (2,6-dimethyl-4-isocyanatocyclohexyl)-1,4,S,6,7,7-

hexachloro-2,5-norbornadiene,

2,3 -bis(4-isocyanatophenyl l ,4,5 ,6,7,7-hexachloro-2,5-

norbornadiene,

2,3-bis (2,6-diisocyanatophenyl) -1,4,5,6,7,7-hexachloro- 2,5-norbornadiene,

2,3-bis (4-isocyanatonaphthyl) l ,4,5,6,7,7-hexachloro-2,5-

nor-bornadiene,

2,3-bis(4-isocyanato-2,6-dimethylphenyl)-1,4,5,6,7,7-

hexachloro-Z,S-norbornadiene,

2,3-bis(4-isocyanatobutoxymethyl)-1,4,5,6,7,7-hexachloro- 2,5-norbornadiene,

2,3-bis(12-isocyanatododecoxymethyl)-1,4,5,6,7,7-

hexachloro-2,5-norbornadiene,

2,3-bis(2,4-diisocyanatophenoxymethyl) -1,4,5,6,7,7-

hexachloro-2,5-norbornadiene,

bis (Z-isocyanatoethyl) 1,4,5,6,7,'7-hexachloro-2,5-

norbornadiene-2,3-dicarboxylate,

bis (3-isocyanatopropyl) 1,4,5 ,6,7,7-hexachloro-2,5-

norbornadiene-2,3-dica.rboxylate,

bis(2,6-diisocyanatophenyl) 1,4,5,6,7,7-hexachloro-2,5-

norbornadiene-2,3-dicarboxylate,

1,4,5 ,6,7,7-hexachloro-2,5-n0rbornadienyl-2,3-dimethyl bis( isocyanatoacetate) 1,4,5 ,6,7,7-hexachloro-2,5-norbornadieneyl-2,B-dimethyl bis(3,5-diisocyanatobenzoate) 2- (2-isocyanatopentyl l ,4,5,6,7,7-hexachloro-2,5-

norbornadiene,

2- 3-isocyanatopropyl -3- (4-isocyanatobuten-2-y1) The novel isocyanates which are embraced Within Formula I supra can be produced by the Diels-Alder reaction of a monoand polyhalogenated cyclopentadiene, e.g. hexachloropentadiene; an alkoxy-substituted halogenated cyclopentadiene, e.g., dimethoxytetrachlorocyclopentadiene; a non-halogenated cyclopentadiene, e.g. cyclopentadiene, methylcyclopentadiene, propylcyclopentadiene; furan; and the like, and an appropriate dienophile. The dienophilic compounds which are suitable for use in the Diels-Alder reaction with the appropriate cyclopentadiene include, among others, those represented by the formulae:

wherein A represents hydrogen, nitro, amino, or isocyanato groups, and wherein R, R R R a, b, n, and m have the meanings set out in Formula I supra.

In those instances wherein A represents hydrogen, the Diels-Alder reaction product can be nitrated, reduced to the amine, and finally reacted with phosgene to obtain the desired isocyanate. In those instances wherein A represents a nitro or amino group, the Diels-Alder product can be converted to the isocyanate by reduction and phosgenation, or merely by phosgenation depending up the group present. In some instances the dienophile may itself contain one or more isocyanate groups so that upon reaction with the appropriate cyclopentadiene compound the novel isocyanate is obtained directly. In other instances, an indirect route may be more practical for economic considerations. For example, the dienophile may contain one or more amino groups which can subsequently be treated with phosgene to obtain the isocyanate after the Diels-Alder reaction is completed. Alternatively, an unsaturated compound containing one or more nitro groups can serve as the dienophile, whereupon after the Diels-Alder reaction is completed, the nitro groups are reduced to the amine by known methods followed by phosgenation to the isocyanate. In some instances wherein it is not economically advantageous or practical to employ a nitro, amino, or isocyanato dienophile, other synthetic routes are available to the appropriate isocyanates. For example, 2-(2,4-diisocyanatophenyl)-1,4,5,6,7,7-hexachloro-5 norbornene was prepared by nitration, reduction and phosgenation of 1,4,5,6,7,7-hexachloro-2-phenylnorborn-S-ene, the Diels- Alder adduct of hexachlorocyclopentadiene with styrene. Nitration was accomplished with a mixture of sulfuric acid and fuming nitric acid. The 2,4-dinitro isomer obtained by recrystallization of the crude nitration product was catalytically hydrogenated to the diamine in acetic acid or isopropanol with platinum oxide catalyst and the diamine, Without isolation, was phosgenated in o-dichlorobenzene solution to alford the corresponding diisocyanate. The unusually inert character of both the chlorine atoms and the aliphatic double bond in adducts of hexachlorocyclopentadiene is strikingly demonstrated by the above reaction sequence. Neither the strongly acidic conditions of nitration nor the vigorous conditions of hydrogenation (acetic acid/platinum oxide) affects these normally-sensitive functional groups.

The reaction of the appropriate cyclopentadiene and unsaturated isocyanate, amino, or nitro compound, as the case may be, can be efiected at a temperature of from about 50 C., to about 250 C., preferably from about 75 C. to about 200 C., for a period of time sufficient to form the composition. Depending upon the choice of reactants and temperature employed, the reaction period may vary from as little as about 1 hour, or less, to about 100 hours, or longer. I

While reaction temperatures within the aforementioned range of from about 50 C. to about 250 C., have been found desirable, temperatures above and below this range can also be employed. However, from economic consideration the optimum yield and rate of reaction are attained within the aforesaid range. The particular temperature employed will be dependent, in part, upon the diene and dienophilic starting material.

The mol ratio of appropriate cyclopentadiene compound to the unsaturated isocyanate, amino, or nitro compound, can vary over a considerable range. For example, a mol ratio of diene to dienophile of from about 0.l:1.0 to about :1.() and more preferably from about 1.0 to 4.0:1.0 can be employed. The pressure employed in the process is not necessarily critical and the reaction can be efiected at atmospheric, subatmospheric or superatmospheric pressures.

In various instances, it may be desirable to conduct the reaction in the presence of an inert, normally liquid organic vehicle, although the use of a vehicle is not required. Suitable vehicles include, among others, aromatic hydrocarbons, such as toluene, xylene, benzene, naphthalene, diphenyl, ethylbenzene; cycloaliphatic hydrocarbons, such as cyclohexane, methylcyclpentane; the chlorinated aromatic hydrocarbons, such as chlorobenzene, orthodichlorobenzene; and the like.

Recovery of the desired reaction product can be eifected 10 by one of many common techniques such as filtration, distillation, extraction, vacuum sublimation, andthe like. Among the unsaturated ester isocyanates which can be employed as the dienophilic component in the Diels-Alder reaction include, among others,

bis(2-isocyanotoethyl) fumarate, bis(3-isocyanatopropyl) glutaconate, bis(Z-isocyanato-l-methylethyl) fumarate, bis(S-isocyanatopentyl) beta-hydromuconate, bis(2,2-dimethyl-3-isocyanatopropyl) fumarate, bis(9-isocyanatononyl) fumarate, bis/(5,6,7-triethyl-9-isocyanatononyl) fumarate, 2-isocyanatoethyl 3-isocyanatopropyl glutaconate, bis(2-isocyanatoethyl) acetylenedicarboxylate, bis(st-isodyanato-Z-butenyl) glutaconate, bis(4-isocyanato-2-butenyl) itaconate, bis(5-isocyanato-3-pentenyl) fumarate, bis(-9-isocyanato-5-nonenyl) itaconate, bis(3,4-dimethyl 5-isocyanato-3-pentenyl) glutaconate, bis(2-methyl-4-ethyl -isocyanato-2Fhexeny1) itaconate, bis(v5,6,7-tirethyl-9-isocyanato-4-nonenyl) glutaconate, 4-isocyanato-2Fbutenyl 3-isocyanatopropyl fumarate, 4-isocyanato-2-butenyl 5-isocyanato-3-pentenyl glutaconate, bis(2-phenyl-3-isocyanatopropyl) fumarate, bis(3-styryl-S-isocyanatopentyl) glutaconate, bis(4-tolyl 6-isocyanatohexyl) itaconate, bis(7-rnesityl-9-isocyanatononyl) glutaconate, bis(2-cyclohexyl-3-isocyanatopropyl) itaconate, bisM cyclohexyl-6-isocyanatohexyl) fumarate, bis(3-cycloheptyl-5-isocyanatopentyl) itaconate, bis(3-cyclohexenyl-5-isocyanatopentyl) glutaconate, bis(2-isocyanatocyclobutyl) fumarate, bis(3-isocyanatocyclopentyl) fumarate, bis(4-isocyanatocyclohexyl) glutaconate, bis(5-isocyanatocycloheptyl) itaconate, bis(3-isocyanato-4-dyclopentenyl) beta-hydromuconate, bis(6-isocyanato-7-cyclooctenyl) fumarate, bis(3-isocyanatocyclopentylmethyl) fumarate, bis(3-isocyanato-2-ethylcyclopentyl) glutaconate, bis(3-isocyanato-5-methylcyclohexyl) fumarate, bis(3-isodyanato-5, 6-dimethylcyclohexyl) glutaconate, bis(3-isocyanato-4,S-diethylcyclopentyl) fumarate, bis 2-isocayanatophenyl) fumarate, bis(3-isocyanatophenyl) glutaconate, bis(7-isocyanato-2-naphthyl) alpha-hydromuconate, bis(7-isocyanato-l-naphthyl) beta-hydromuconate, bis(4-isodyanato-4-biphenylyl) itaconate, bis(5-isocyanato-2-indenyl) maleate, bis(4-isocyanatobenzyl) fumarate, bis(7-isocyanatonaphthylmethyl) itaconate, bis[4(3'-isocyanatopropyl)phenyl] maleate, bis(4-isocyanatomethylphenyl) fumarate, bis[2(3'-isocyanatopropyl)naphthyl] glutaconate, =bis(4-isocyanato-2-methylphenyl) alpha-hydromuconate, bis(4-isocyanato-3-cumenyl) fumarate, bis(4-isocyanato-Z-methoxyphenyl) glutaconate, bis(4-isocyanatostyryl) itaconate, bis(4-isocyanatocinnamyl) fumarate, bis[4(4'-isocyanato2'-butenyl)phenyl] glutaconate,

and the like.

Although the preferred diisocyanates of this invention contain no elements other than carbon, hydrogen, oxygen and nitrogen, the molecule can be substituted with various organic and inorganic radicals containing such groups as ether, sulfide, polysulfide, sulfone, sulfoxide, ester, nitro, nitrile, and carbonate groups.

The bicycloalkenyl dienophiles, e.g., Z-isocyanatomethylnorborn-5-ene, are prepared by the Diels Alder reaction of cyclopentadiene and an appropriate, dienophile, e.g., allylamine. The preparation of these compounds is the subject matter of an application entitled Novel Unsaturated Isocyanates And Process For Preparation by T. K. Brotherton and J. W. Lynn, Ser. No. 88,279, filed Feb. 10,

1 1 1961, now US. Pat. No. 3,141,900, and assigned to the same assignee as the instant invention.

The olefinically unsaturated isocyanates which are employed in preparing the novel compositions of this invention are themselves prepared by the reaction of the corresponding ester diamine dihydrohalide with a carbonyl dihalide. The preparation of the olefinically unsaturated ester isocyanates, such as bis(2-isocyanatoethyl) fumarate, bis(4-isocyanatophenyl) fumarate, and the like, is the subject matter of an application entitled Novel Olefinically Unsaturated Diisocyanates and Process for Preparation by T. K. Brotherton and J. W. Lynn, Ser. No. 212,480, filed July 25, 1962, and assigned to the same assignee as the instant invention and now abandoned.

In general, the conversion of the ester diamine salt to the ester diisocyanate is accomplished by sparging a carbonyl dihalide, more preferably phosgene, through a slurry of the ester diamine dihydrohalide contained in an inert, normally liquid reaction medium at a temperature within the range of from about 100 C. to about 225 C., more preferably from about 125 C. to about 170 C., and thereafter recovering the ester diisocyanate. In either instance, it is believed that the intermediate carbamoyl chloride is first formed from the free amine and subsequently thermally degraded to the diisocyanate at the reaction temperature employed. The process can be conducted in either a batch type or continuous reactor.

The preparation of the olefinically unsaturated ester diamine hydrohalide, such as bis(2-aminoethyl) fumarate dihydrohalide, bis(4-aminophenyl) fumarate dihydro halide, and the like is the subject matter of an application entitled Novel Amino Esters of Olefinically Unsaturated Polycarboxylic Acids and Process for Preparation by T. K. Brotherton and J. W. Lynn, Ser. No. 212,481, filed July 25, 1962, and assigned to the same assignee as the instant invention and now abandoned.

The starting materials can be prepared, as indicated in the examples, and in the aforementioned copending application, by the reaction of an olefinically unsaturated polycarboxylic acid halide, such as fumaryl chloride, and a hydroxy amine hydrohalide, such as monoethanolamine hydrohalide, at a temperature of from about 65 to about 95 C., for several hours. The ester diamine dihydrohalide is then isolated, as for example, by filtration and then washed and dried. By the aforementioned process the ester diamine dihydrohalides can be obtained in yields of about 95 percent and higher. For further information regarding the production of the ester diamines hydrohalides reference is hereby made to the disclosure of the aforementioned application.

The novel isocyanates are an extremely useful class of compounds which possess exceptionally attractive and outstanding properties. The reaction products of the novel aliphatic isocyanates are highly resistant to sunlight or ultra-violet light degradation. Many of the novel isocyanates are virtually nonlachrymators. Moreover, several of the novel isocyanates are relatively inexpensive compounds which may readily compete with commercially available diisocyanates.

Of significance with regard to many of the novel isocyanates are their ability to undergo both vinyl polymerization and isocyanate condensation polymerization. For example, the novel polymerizable ethylenically unsaturated isocyanates can be homopolymerized or copolymerized with a host of ethylenically unsaturated compounds, e.g., styrene, vinyl chloride, butadiene, isoprene, chloroprene, ethyl acrylate, methyl acrylate, etc., through a polymerizable ethylenic bond of the reactant(s), under conventional vinyl polymerization conditions, to give polymers of varying molecular weight which contain a plurality of pendant or free isocyanato groups. The resulting polyisocyanato-containing polymers then can be subjected to isocyanate condensation polymerization reactions with an active polyhydrogen compound, e.g., polyol, polyamine, etc., to give useful three dimensional, crosslinked solid products which can be termed poly(vinyl urethanes), poly(vinyl ureas), etc., depending on the active hydrogen compound employed.

The reaction of the novel polymerizable ethylenically unsaturated isocyanates of Formula I supra, on the other hand, with an active monohydrogen compound, e.g., monoamine, alkanol, etc., results in novel ethylenically unsaturated compounds which in turn can be polymerized with an ethylenically unsaturated organic compound which contains at least one polymerizable ethylenic bond (through the polymerizable carbon to carbon double bond) to yield a myriad of polymeric products.

Isocyanate condensation polymerization reactions involving a difunctional compound such as a diol, diamine, etc., with the novel polyethylenically unsaturated diisocyanates of Formula I can yield linear polyethylenically unsaturated polymeric products which products can be crosslinked to useful solids by reaction with olefins, e.g., divinylbenzene, butadiene, and the like.

Crosslinked poly(vinyl urethanes) can also be prepared via a one shot process which involves concurrent vinyl and condensation polymerization reactions.

Thus, it is apparent that the novel polymerizable ethylenically unsaturated isocyanates permit the wedding of low costly vinyl monomers, i.e., ethylenically unsaturated organic monomers which contain at least one polymerizable ethylenic bond, with high performance polyurethanes, polyureas, and the like. This advantage has significance in the development of a myriad of products (based on several of the novel isocyanates) which have exceptionally strong commercial and economic attractiveness.

A most noteworthy feature of the novel isocyanates, in particular the novel chlorinated polyisocyanates, is their exceptional ability to impart into products such as foams, coatings, castings, reinforced plastics, elastomers, etc., outstanding characteristics and properties. Moreover, the low cost of many of the novel hexachlorinated isocyanates makes them potentially commercially attractive in, for example, the urea and/ or urethane fields.

In many instances, novel pourable polyisocyanates such as the hexachlorinated 2,3 bis(isocyanatoalkyl) 5 norbornene-2,3 dicarboxylates, e.g., bis-(2-isocyanatoethyl) 1,4,5,6,7,7-hexachloro-S-norbornene 2,3 dicarboxylate, can be employed in the preparation of flame-retardant foams, especially rigid foams, which exhibit the characteristic of charring rather than dripping during the burning test. The novel hexachlorinated polyisocyanates in admixture with polyisocyanates especially those produced by the phosgenation of the reaction products of aniline and formaldehyde represent a particularly attractive aspect of the invention as will become apparent hereinafter.

In one aspect, the invention is directed to the preparation of novel products which result from the reaction of the novel isocyanates such as those exemplified by Formula I with compounds which contain at least one reactive hydrogen as determined according to the Zerewitinoff test described by Wohler in the Journal of the American Chemical Society, volume 48, p. 3181 (1927). Illustrative classes of compounds which contain at least one active hydrogen include, for instance, alcohols, amines, carboxylic acids, phenols, ureas, urethanes, hydrazines, water, ammonia, hydrogen sulfide, imines, thiourea, sulfimides, amides, thiols, amino alcohols, sulfonamides, hydrazones, semi-carbazones, oximes, hydroxycarboxylic acids, aminocarboxylic acids, vinyl polymers which contain a plurality of pendant active hydrogen substituents such as hydroxyl or amino, and the like. In addition, the hydrogen substituent may be activated by proximity to a carbonyl group. The active hydrogen organic compounds represent a preferred class.

Illustrative of the aforesaid active hydrogen compounds are the hydroxyl-containing compounds, especially those which possess at least one alcoholic hydroxyl group and preferably at least two alcoholic hydroxyl groups. Typical compounds include, for instance, the monohydric alcohols such as methanol, ethanol, propanol, isopropanol, l-butanol, allyl alcohol, Z-butanol, tert-butanol, 3-butenol, lpentanol, 3-pentano1, l-hexanol, hex-S-en-l-ol, 3-heptanol, Z-ethyl-l-hexanol, 4-nonanol, propargyl alcohol, benzyl alcohol, cyclohexanol,cyclopentanol, cycloheptanol, and trimethylcyclohexanol. Further alcohols contemplated include the monoesterified diols such as those prepared by the reaction of equimolar amounts of an organic monocarboxylic acid, its ester, or its halide, with a diol such as alkylene glycols, monoand polyether diols, monoand polyester diols, etc., e.g.,

Rl i 0 R OH wherein is acyl and R is a divalent organic radical containing at least two carbon atoms in the divalent chain; the monoetherified diols such as those represented by the formula R OROH wherein R represents a monovalent organic radical such as a hydrocarbyl or oxahydrocarbyl radical and R has the aforesaid value; the mono-ols produced by the partial esterification reaction of a polyol containing at least three hydroxyl groups, e.g., glycerine, with a stoichiometric defiiciency of an organic monocarboxylic acid, its ester, or acyl halide; and the like. The aforesaid reaction are well documented in the literature.

Polyhydric alcohols can be exemplified by polyols of the formula HO-R-OH wherein R is a divalent hydrocarbyl radical or a monoor polyhydroxy substituted hydrocarbyl radical, the aforesaid formula hereinafter being referred to as alkylene polyols (when they possess two or more hydroxy groups) or alkylene glycols (when they possess two hydroxy groups). Other polyhydric alcohols can be represented by the formula HOR OH wherein R is a substituted or unsubstituted (alkyleneoxy) alkylene radical with n being an integer of at least one. This latter formula will hereinafter be referred to as polyether polyols (when they contain at least two hydroxy groups) or polyether glycols (when they contain two hydroxy groups). The variables R and R have at least two carbon atoms in the linear chain, and the substituents or pendant groups on these variables can be, for example, lower alkyl, halo, lower alkoxy, etc., such as methyl, ethyl, n-propyl, isopropyl, chloro, methoxy, ethoxy, and the like. Illustrative alkylene polyols and polyether polyols include ethylene glycol; butylene glycol; 2,2- diethyl-l,3-propanediol; 2,2-diethyl 1,3 propanediol; 3- methyl-1,5-pentanediol; 2-butene 1,4 diol; the polyoxyalkylene glycols such as diethylene glycol, dipropylene glycol, di-butylene glycol, polyoxytetramethylene glycol, and the like; the mixed monoand polyoxyalkylene glycols such as the monoand polyoxyethyleneoxypropylene glycols, the monoand polyoxyethyleneoxybutylene glycols, and the like; polydioxolane and polyformals prepared by reacting formaldehyde with other glycols or mixtures of glycols, such as tetramethylene glycol and pentamethylene glycol; and the like. Other polyols include the N-methyland N-ethyl-diethanolamines; 4,4'-methyl-enebiscyclohexanol; 4,4-isopropylidenebiscyclohexanol; butyne-1,4-diol; the hydroxymethyl substituted phenethyl alcohols; the ortho-, meta-, and para-hydroxymethylphenylpropanols; the various phenylenediethanols, the various phenylenediproponals, the various heterocyclic diols such as 1,4- piperazinediethanol; and the like. The polyhydroxyl-containing esterification products which range from liquid to non-crosslinked solids, i.e., solids which are soluble in many of the more common inert normally liquid organic media, and which are prepared by the reaction of monocarboxylic acids and/or polycarboxylic acids, their anhydrides, their esters, or their halides, with a stoichiornetric excess of a polyol such as the various diols, triols, etc.;

illustrated previously, are highly preferred. The aforesaid polyhydroxyl-containing esterification products will hereinafter be referred to as polyester polyols. Those polyester polyols which contain two alcoholic hydroxyl groups will hereinafter be termed polyester diols. Illustrative of the polycarboxylic acids which can be employed to prepare the polyester polyols preferably include the dicarboxylic acids, tricarboxylic acids, etc., such as maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, chlorendic acid, 1,2,4-butanetricarboxylic acid, phthalic acid, etc. This esterification reaction is well documented in the literature.

Higher functional alcohols suitable for reaction with the novel isocyanates include the triols such as glycerol, 1,1,l-trimethylolpropane, 1,2,4-butanetriol, 1,2,6-hexanetriol, triethanolamine, triisopropanolamine, and the like;

the tetrols such as erythritol, pentaerythritol, N,N,N,N'- tetrakis(2-hydroxyethyl)ethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediarnine, and the like; the pentols; the hexols such as dipentaerythritol, sorbitol, and the like; the alkyl glycosides such as the methyl glucosides; the carbohydrates such as glucose, sucrose, starch, cellulose, and the like.

Other suitable hydroxyl-containing compounds include the monoand the polyoxyalkylated derivatives of monoand polyfunctional compounds having at least one reactive hydrogen atom. These functional compounds may contain primary or secondary hydroxyls, phenolic hydroxyls, primary or secondary amino groups, amide, hydrazino, guanido, ureido, mercapto, sulfino, sulfonamido, or carboxyl groups. They can be obtained by reacting, (1) monohydric compounds such as aliphatic and cycloaliphatic alcohols, e.g., alkanol, alkenol, methanol, ethanol, allyl alcohol, 3-buten-1-ol, 2-ethylhexanol, etc.; diols of the class HOt-R-l Ol-l and HOt-RO-ROhH wherein R is alkylene of 2 to 4 carbon atoms, and wherein n equals 1 to 10 such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and the like; thiodiethanol; the xylenediols, 4,4' methylene-diphenol, 4,4'-isopropylidenediphen01, resorcinol; and the like; the mercapto alcohols such as mercaptoethanol; the dibasic acids such as maleic, succinic, glutaric, adipic, pimelic, sebacic, phthalic, tetrahydrophthalic, and hexahydrophthalic acids; phosphorous acids; phosphoric acids; the aliphatic, aromatic, and cycloaliphatic primary monoamines, like methylamine, ethylamine, propylamine, butylamine, aniline, and cyclohexylamine; the secondary diamines like N,N-dimethylethylenediamine; and the amino alcohols containing a secondary amino group such as N-methylethanolamine; with (2) vicinal monoepoxides as exemplified by ethylene oxide, 1,2-epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, isobutylene oxide, butadiene monoxide, allyl glycidyl ether, 1,2-epoxyoctene-7, styrene oxide, and mixtures thereof.

Further examples of polyols are the polyoxyalkylated derivatives of polyfunctional compounds having three or more reactive hydrogen atoms such as, for example, the reaction products (adducts) of 1,1,1-trimethylolpropane with a lower vicinal-epoxyalkane, e.g., ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof, in accordance with the reaction:

wherein Jd+y+z equals 3 to 45, and more.

In addition to the polyoxyalkylated derivatives of 1,1,1- trimethylolpropane, the following illustrative compounds are likewise suitable: 1,1,l-trimethylolethane; glycerol; 1,2,4-butanetriol; 1,2,6-hexanetriol; erythritol; pentaerythritol; sorbitol; the alkyl glycosides such as the methyl glucosides; glucose; sucrose; the diamines of the general formula H N(CH- NH where n equals 2 to 12; 2- (methylamino)ethylamine; the various phenyleneand toluene-diamines; benzidine; 3,3'-dimethyl-4,4'-biphenyldiamine; 4,4'-methy1enedianiline; 4,4',4"-methylidynetrianiline, the cycloaliphatic diamines such as 2,4-cyclhexanediamine, and the like; the amino alcohols of the general formula HO(CH ),,NH where n equals 2 to the polyalkylenepolyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and the like; the polycarboxylic acids such as citric acid, aconitic acid, mellitic acid, pyromellitic acid, and the like; and polyfunctional inorganic acids like phosphoric acid. The aforesaid polyfunctional polyoxyalkylated compounds will be referred to hereinafter as polyoxyalkylated polyols. The polyoxyalkylated polyols which contain two alcoholic hydroxyl groups will be termed polyoxyalkylated diols Whereas those which contain a sole alcoholic hydroxyl group will be referred to as polyoxyalkylated mono-01s.

Illustrative amino-containing compounds which are contemplated are those which contain at least one primary amino group (NH or secondary amino group (NHR wherein R is hydrocarbyl such as alkyl, aryl, cycloalkyl, alkaryl, aralkyl, etc.), or mixtures of such groups. Preferred amino-containing compounds are those which contain at least two of the above groups. Illustrative of the amino-containing compounds include the aliphatic amines such as the alkylamines, e.g., the methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, sec-butyl-, isobutyl-, tert-butyl-, n-amyl-, n-hexy1-, and 2-ethylhexylamines, as well as the corresponding dialkylamines; the aromatic amines such as aniline, ortho-toluidine, meta-toluidine, and the like; the cycloaliphatic amines such as cyclohexylamine, dicyclohexylamine, and the like; the heterocyclic amines such as pyrrolidine, piperidine, morpholine, and the like; the various aliphatic diamines of the general formula H N(CH ),,NH monosecondary diamines of the general formula R"NH(CH ),,NH, and disecondary diamines of the general formula R"NH(CH NHR", where n equals 2 to 10, and more, and where R" is hydrocarbyl such as alkyl, aryl, aralkyl, alkaryl, or cycloalkyl; the etheric diamines of the formula wherein n is an integer of 2 to 10, and wherein R is alkylene or oxaalkylene of 2 to 10 carbon atoms; the aromatic diamines such as meta-phenylene-diamine, para-phenylenediamine, toluene-2,4-diamine, toluene-2,6-dia mine, 1,5- naphthalenediamine, 1,8-naphthalenediamine, meta-xylylenediamine, para-xylylenediamine, benzidine, 3,3-dimethyl-4,4-biphenyldiamine, 3,3'-dimethoxy-4,4-biphenyl-diamine, 3,3-dichloro-4,4'-biphenyldiamine, 4,4'-methylenedianiline, 4,4'-methylene-bis(ortho-chloroaniline), 4,4- ethylenedianiline, 2,3,5,6-tetramethyl-para-phenylenediamine, 2,5-fluorenediamine, and 2,7-fluorenediamine; the cycloaliphatic diamines such as 1,4-cyclohexanediamine, 4,4'- methylenebiscyclohexylamine, and 4,4'-isopropylidenebiscyclohexylamine; and the heterocyclic amines such as piperazine, 2,5-dimethylpiperazine, 1,4-bis(3-aminopropyl)piperazine, and the like.

Illustrative of the higher functional amino-containing compounds which can be employed include, for example, higher polyalkylenepolyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, and the like; 1,2,5-benzenetriamine; toluene-2,4,6-triamine; 4,4,4"-methylidynetrianiline; and the like; the polyamines obtained by interaction of aromatic monoamines with formaldehyde or other aldehydes, for example:

and other reaction products of the above general type, where R is, for example, hydrogen or alkyl.

Illustrative of the carboxyl-containing compounds include those organic compounds which contain at least one carboxyl group (COOH) as exemplified by the rnonocarboxyl-containing compounds such as alkanoic acids; the cycloalkanecarboxylic acids; the monoesterified dicarboxylic acids, e.g.,

wherein R is an organic radical such as oxahydrocarbyl, hydrocarbyl, etc., and R is the divalent residue of a dicarboxylic acid after removal of the two dicarboxylic groups; the polycarboxylic acids, e.g., the aliphatic, cycloaliphatic, and aromatic dicarboxylic acids; and the like. Specific examples include propionic acid, butyric acid, valeric acid, dodecanoic acid, acrylic acid, cyclohexanecarboxylic acid, the mono-Z-ethylhexyl ester of adipic acid, succini acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic aid, chlorendic acid, 4,4-oxydibutyric acid, 5,5'-oxydiva1leric acid, 6,6'-oxydihexanoic acid, 4,4'-thiodibutyric acid, 5,S'-thiodivaleric acid, 6,6" thiodihexanoic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, the tetrachlorophthalic acids, 1,5 naphthoic acid, 2,7-naphthoic acid, 2,6 naphthoic acid, 3,3-methylenedibenzioic acid, 4,4 (ethylenedioxy)dibenzoic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-sulfonyldibenzoic acid, 4,4-oxydibenzoic acid, 4,4-oxydibenzoic acid, the various tetrahydrophthalic acids, the various hexahydrophthalic acids, tricarballylic acid, aconitic acid, citric acid, hemimollitic acid, 'trimellitic acid, trimesic acid, pyromellitic acid, 1,2,3, 4-bu-tanetetracarboxylic acid, and the like. The polycarboxyl-containing esterification products which range from liquid to non-crosslinked solids and which are prepared by the reaction of polycarboxylic acids, their anhydride, their esters, or their halides, with a stoichiometric deficiency of a polyol such as diols, triols, etc., can also be employed. These polycarboxyl-containing esterification products will hereinafter be referred to as polycarboxy polyesters.

Compounds which contain at least two different gioups of the class of amino (primary or secondary), carboxyl, and hydroxyl, and preferably those which contain at least one amino group and at least one hydroxyl group, can be exemplified by the hydroxycarboxylic acids, the aminocarboxylic acids, the amino alcohols, and the like. Illustrati=ve examples include Z-hydroxypropionic acid, 6-hydroxycaproic acid, ll-hydroxyundecanoic acid, salicyclic acid, para-hydroxybenzoic acid, beta-alanine, 6-aminocaproic acid, 7-aminoheptanoic acid, ll-aminoundecanoic acid, para-aminobenzoic acid, and the like; the amino alcohols of the general formula HO (CHQ NH where n equals 2 to 10; other hydroxyalkylamines such as N- methylethanolamine, isopropanolamine, N-methylisopropanolamine, and the like; the aromatic amino alcohols like para-amino-phenethyl alcohol, para-amino-alphamethylbenzyl alcohol, and the like; the various cycloaliphatic amino alcohols such as 4-aminocyclohexanol,

17 and the like; the higher functional amino alcohols having a total of at least three hydroxy and primary or secondary amino groups such as the dihydroxyalkylarnines, e.g., diethanolamine, diisopropanol amine, and the like; 2 (Z-ann'no ethylamino)ethanol; 2Famino-2-(hydroxymethyl)-l,3-propanediol; and the like.

The initiated lactone polyesters which contain free hydroxyl group(s) and/or carbonyl group(s) represent extremely preferred active hydrogen containing compounds. These initiated lactone polyesters are formed by reacting, at an elevated temperature, for example, at a temperature of from about 50 C. to about 250 C., an admixture containing a lactone and an organic initiator; said lactone being in molar excess with relation to said initiator; said lactone having from six to eight carbon atoms in the lactone ring and at least one hydrogen substituent on the carbon atom which is attached to the oxy group in said ring; said organic initiator having at least one reactive hydrogen substituent preferably of the group of hydroxyl, primary amino, secondary amino, carboxyl, and mixtures thereof, each of said reactive hydrogen substituents being capable of opening the lactone ring whereby said lactone is added to said initiator as a substantially linear group thereto; said initiated lactone polyesters possessing, on the average, at least two of said linear groups, each of said linear groups having a terminal oxy group at one end, a carbonyl group at the other end, and an intermediate chain of from five to seven carbon atoms which has at least one hydrogen substituent on the carbon atom in said intermediate chain that is attached to said terminal oxy group. The aforesaid polyesters will hereinafter be referred to, in the generic sense, as initiated lactone polyesters which term will also include the various copolymers such as lactone copolyesters, lactone polyester/polycarbonates, lactone polyester/polyethers, lactone polyester/polyether/polycarbonates, lactone polyester/ polyester, etc. These initiated lactone polyesters will contain at least one hydroxyl group and/or at least one carboxyl group depending, of course, on the initiator and reactants employed. Those initiated lactone polyesters which contain at least three alcoholic hydroxyl groups will be referred to as initiated lactone polyester polyols; those with two alcoholic hydroxyl groups will be termed initiated lactone polyester diols. On the other hand, the initiated lactone polyesters which contain at least two carboxyl groups will be referred to as initiated polycarboxy lactone polyesters.

The preparation of the aforesaid hydroxyl-containing and/or carboxyl-containing initiated lactone polyesters can be elfected in the absence or presence of an ester interchange catalyst to give initiated lactone polyesters of widely varying and readily controllable molecular weights without forming water of condensation. These lactone polyesters so obtained are characterized by the presence of recurring linear lactone units, that is, carbonylakyleneoxy (0 R2) :CHRO-1 wherein x is from 4 to 6, and wherein the 'R variables have the values set out in the next paragraph.

The lactone used in the preparation of the initiated lactone polyesters may be any lactone, or combination of lactones, having at least six carbon atoms, for example, from six to eight carbon atoms, in the ring and at least one hydrogen substituent on the carbon atom which is attached to the oxy group in said ring. In one aspect, the lactone used as starting material can be represented by the general formula:

Ro11 om ,.o=o

in which n is at least four, for example, from four to six,

at least n+2Rs are hydrogen, and the remaining Rs are substituents selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy and single ring aromatic hydrocarbon radicals. Lactones having greater number of substituents other than hydrogen on the ring, and lactones having four carbon atoms in the ring, are considered unsuitable because of the tendency that polymers thereof have to revert to the monomer, particularly at elevated temperature.

The lactones which are preferred in the preparation of the hydroxyl-containing and/or carboxyl-containing initiated lactone polyesters are the epsilon-caprolactones having the general formula:

wherein at least six of the R variables are hydrogen and the remainder are hydrogen, alkyl, cycloalkyl, alkoxy, or single ring aromatic hydrocarbon radicals, none of the substituents contain more than about twelve carbon atoms, and the total number of carbon atoms in the substituents on the lactone ring does not exceed about twelve.

Among the substituted epsilon-caprolactones considered most suitable are the various monoalkyl epsiloncaprolactones such as the monomethyl-, monoethyl-, monopropyl-, monoisopmpyl-, etc. to monododecyl epsilon caprolactones; dialkyl epsilon-caprolactones in which the two alkyl groups are substituted on the same or different carbon atoms, but not both on the epsilon carbon atom; trialkyl epsilon-caprolactones in which two or three carbon atoms in the lactone ring are substituted, so long as the epsilon carbon atom is not disubstituted; alkoxy epsilon-caprolactones such as methoxy and ethoxy epsilon-caprolactones; and cycloalkyl, aryl, and aralkyl epsilon-caprolactones such as cyclohexyl, phenyl and benzyl epsilon-caprolactones.

Lactones having more than six carbon atoms in the ring, e.g., zeta-enantholactone and eta-caprylolactone can be employed as starting material. Mixtures comprising the C to C lactones illustrated previously, with/without, for instance, the alpha, alpha disubstituted-beta-propiolactones, e.g., alpha, alpha-dimethyl-beta-propiolactone, alpha, alpha-dichloromethyl beta-propiolactone, etc.; with/ without, for instance, oxirane compounds, e.g., ethylene oxide, propylene oxide, etc.; with/without, for instance, a cyclic carbonate, e.g., 4,4-dimethyl-2,6-dioxacyclohexanone, etc.; are also contemplated.

Among the organic initiators that can be employed to prepare the initiated lactone polyesters include the carboxyl-containing, hydroxyl-containing, and/or aminocontaining compounds illustrated previously, e.g., those compounds which have at least one reactive hydrogen substituent as determined according to the Zerewitinotf method.

The initiator is believed to open the lactone ring to produce an ester or amide having one or more terminal :groups that are capable of opening further lactone rings and thereby adding more and more lactone units to the growing molecule. Thus, for example, the polymerization of epsilon-caprolactone initiated with an amino alcohol is believed to take place primarily as follows:

O HORNHQXCHMOH wherein R (of the initiator and the resulting initiated lactone polyester product) is an organic radical such as an aliphatic, cycloaliphatic, aromatic, or heterocyclic radical, and wherein a=b+c.

The reaction of a carboxyl-containing initiator with epsilon-caprolactone is believed to proceed as follows:

It will be appreciated from the preceding illustrative equations that where a plurality of lactone units are linked together, such linkage is effected by monovalent bonding the oxy (O-) moiety of one unit to the carbonyl moiety of an adjacent unit. The terminal lactone unit will have a terminal hydroxy or carboxyl end group depending, of course, on the initiator employed.

The preparatioin of the initiated lactone polyester can be carried out in the absence of a catalyst though it is preferred to effect the reaction in the presence of an ester exchange catalyst. The organic titanium compounds that are especially suitable as catalysts include the tetraalkyl titanates such as tetraisopropyl titanate and tetrabutyl titanate. Additional preferred catalysts include, by way of further examples, the stannous diacylates and stannic tetraacylates such as stannous dioctanoate and stannic tetraoctanoate. The tin compounds, the organic salts of lead and the organic salts of manganese which are described in U.S. 2,890,208 as well as the metal chelates and metal acylates disclosed in U.S. 2,878,236 also represent further desirable catalysts which can be employed. The disclosures of the aforesaid patents are incorporated by reference into this specification.

The catalysts are employed in catalytically significant concentration. In general, a catalyst concentration in the range of from about 0.0001 and lower, to about 3, and higher, weight percent, based on the weight of total monomeric feed, is suitable. The lactone polymerization reaction is conducted at an elevated temperature. In general, a temperature in the range of from about 50 C., and lower, to about 250 C. is suitable; a range from about 100 C. to about 200 C. is preferred. The reaction time can vary from several minutes to several days depending upon thet variables illustrated immediately above. By employing a catalyst, especially the more preferred catalysts, a feasible reaction period would be about a few minutes to about hours, and longer.

The polymerization reaction preferably is initiated in the liquid phase. It is desirable to effect the polymerization reaction under an inert atmosphere, e.g., nitrogen.

The preparation of the lactone polyesters via the preceding illustrative methods has the advantage of permitting accurate control over the average molecular weight of the lactone polyester products and furtherof promoting the formation of a substantially homogeneous lactone polyester in which the molecular weights of the individual molecules are reasonably close to the average molecular weight, that is, a narrow molecular weight distribution is obtained. This control is accomplished by preselecting the molar proportions of lactone and initiator in a manner that will readily be appreciated by those skilled in the art. Thus, for example, if it is desired to form a lactone polyester in which the average molecular weight is ap proximately fifteen times the molecular weight of the initial lactone, the molar proportions of lactone and intiator utilized in the polymerization reaction are fixed at approximately :1 inasmuch as it is to be expected that on the average there will be added to each molecule of initiator approximately fifteen lactone molecules.

The initiated lactone polyesters which are contemplated have average molecular weights as low as 300 to as high as about 7000, and even higher still to about 9000. With vinyl polymers containing a plurality of active hydrogen substituents, e.g., hydroxyl, amino, etc., as initiators, the average molecular weight of the initiated lactone polyesters can easily go as high as 14,000, and higher. Generally, however, the average molecular weight of the initiated lactone polyester is from about 300 to about 9000, preferably from 600 to about 5000.

As intimated previously, also within the term and the scope of the initiated lactone polyesters are those in which the linear lactone units need not necessarily be connected directly to one another. This is readily accomplished, for example, by reacting lactone(s) with combinations of initiators such as dibasic acid(s) plus glycol(s), diamine(s) or amino alcohol(s) such as those exemplified previously. This reaction can be effected at an elevated temperature, e.g., about C. to about 200 C., with all the reactants present, or the reaction of the dibasic acid with the glycol, diamine, or amino alcohol can be accomplished first, and then the resulting amino-, hydroxyl-, or carboxyl-containing products (depending on the reactants and the concentration of same) can be reacted with the lactone to yield hydroxyl-terminated and/or carboxyl-terminated initiated lactone polyesters. Moreover, as also indicated previously, the term and the scope of the hydroxyland/ or carboxyl-containing initiated lactone polyesters includes the oxyalkylene-carboxyalkylene such as described in U.S. Pat. No. 2,962,524 which are incorporated by reference into this disclosure. In addition the term and scope of the hydroxyl-containing initiated lactone polyesters also includes the reaction of an admixture comprising a C C lactone(s), a cyclic carbonate(s), and an initiator having at least one group, preferably at least two groups, of the class of hydroxyl, primary amino, or secondary amino, or mixtures thereof, under the operative conditions discussed above. Exemplary cyclic carbonates include 4,4-dimethyl-2,6-dioxacyclohexanone, 4,4-dichloromethyl-2,6-dioxacyclohexanone, 4,4-dicyanomethyl-2,6-dioxacyclohexanone, 4,4-diethyl-2,6-dioxacyclohexanone, 4,4-dimethoxymethyl-2,6- dioxacyclohexanone; and the like. Consequently, where a mixture of linear lactone units (i.e.,

o 1(CR2)4CHRO units which are properly termed carbonylalkyleneoxy) and linear carbonate units (i.e.

o -(.i OR 0- units which can be termed carbonyloxyalkyleneoxy) are contained in the polymer chain or backbone, the carbonyl moiety of one linear unit will be monovalently bonded to the oxy moiety of a second linear unit. The oxy moiety of a terminal linear unit will be bonded to a hydrogen substitutent to thus form a hydroxyl end group. Moreover, the point of attachment of the initiator and a linear unit (lactone or carbonate) will be between the carbonyl moiety of said unit and the functional group (hydroxyl or amino) of said initiator sans the active hydrogen substitutent of said group.

The preferred initiated lactone polyesters include those which contain at least about 25 mol percent (and preferably at least about 50 mol percent) of carbonylpentamethyleneoxy units therein 0 2)5 and which possess an average molecular weight of from about to about 5000, particularly from about 500 to about 4000. The remaining portion of the molecule may be comprised of in addition to the initiator, essentially linear units derived from a cyclic carbonate especially those illustrated previously; an oxirane compound especially ethylene oxide, propylene oxide, and/or the butylene oxides; a monoand/or polyalkyl-substituted epsiloncaprolactone especially the monoand/or polymethyl and or ethyl-substituted epsilon-caprolactones; and/ or an alpha, alpha-disubstituted-beta-propiolactonc especially those exemplified previously. The so-called initiated lactone homopolyesters derived from reacting epsilon-caprolactone with an initiator are likewise included within the preferred lactone polyesters. The initiated lactone polyester polyols, and in particular, the substantially linear initiated lactone polyester diols, are exceptionally preferred.

If desired, various compounds can be employed as catalysts in the isocyanato/active hydrogen reactions. Compounds which are oftentimes useful in catalyzing said isocyanato-active hydrogen reactions include the tertiary amines, phosphines, and 'various organic metallic compounds in which the metal can be bonded to carbon and/ or other atoms such as oxygen, sulfur, nitrogen, halo, hydrogen, and phosphorus. The metal moiety of the organic metallic compounds can be, among others, tin, titanium, lead, potassium, sodium, arsenic, antimony, bismuth, manganese, iron, cobalt, nickel, and zinc. Of those which deserve special mention are the organic metallic compounds which contain at least one oxygen to metal bond and/or at least one carbon to metal bond, especially wherein the metal moiety is tin, lead, bismuth, arsenic, or antimony. The tertiary amines, the organic tin compounds (which includes the organotin compounds), and the organic lead compounds are eminently preferred. Preferred subclasses of organic metallic compounds include the acylates, particularly the alkanoates, and alkoxides of Sn(II), Sn(IV), Pb(II), Ti(1V), Zn(IV), Co(II), Mn(lI[), Fe'(FII), Ni(II), K, and Na. An additional subclass which is extremely useful is the dialkyltin dialkanoates.

Inorganic metallic compounds such as the hydroxides, oxides, halides, and carbonates of metals such as the alkali metals, the alkaline earth metals, iron, zinc, and tin are also suitable.

Specific catalysts include, by way of illustrations, 1,4- diazabicyclo [2.2.2]octane, N,N,N',N' tetramethyl 1,3- butanediamine, bis[2-(N,N-dimethylamino)ethyl] ether, bis[2 (N,N dimethylamino) l-methylethyl] ether, N- methylmorpholine, sodium acetate, potassium laurate, stannous octanoate, stannous oleoate, lead octanoate, tetrabutyl titanate, ferric acetylacetonate, cobalt naphthenate, tetramethyltin, tributyltin chloride, tributyltin hydride, trimethyltin hydroxide, dibutyltin oxide, dibutyltin dioctanoate, dibutyltin dilaurate, butyltin trichloride, triethylstibine oxide, potassium hydroxide, sodium carbonate, magnesium oxide, stannous chloride, stannic chloride, bismuth nitrate. Other catalysts include those set forth in Part IV. Kinetics and Catalysis of 'Reactions of Saunders, et al. Polyurethanes: Chemistry and TechnologyPart I. Chemistry, Interscience Publishers, which is incorporated by reference into this disclosure. In many instances, it is particularly preferred to employ combinations of catalysts such as, for example, a tertiary amine plus an organic tin compound.

The isocyanato-reactive hydrogen reactions can be conducted over a wide temperature range. In general, a temperature range of from about to about 250 C. can be employed. To a significant degree, the choice of the reactants and catalyst, if any, influences the reaction temperature. Of course, stcrically hindered novel isocyanates or active hydrogen compounds will retard or inhibit the reaction. Thus, for example, the reaction involving isocyanato with primary amino or secondary amino can be effected from about 0 C. to about 250 C. whereas the isocyanato-phenolic hydroxyl reaction is more suitably conducted from about 30 C. to about 150 C. Reactions involving primary alcoholic hydroxyl, secondary alcoholic hydroxyl, or carboxyl with isocyanato are effectively conducted from about 20 C. to about 250 C. The upper limit of the reaction temperature is selected on the basis of the thermal stability of the reaction products and of 22 the reactants whereas the lower limit is influenced, to a significant degree, by the rate of reaction.

The time of reaction may vary from a few minutes to several days, and longer, depending upon the reaction temperature, the identity of the particular active hydrogen compound and isocyanate as well as upon the absence or presence of an accelerator or retarder and the identity thereof, and other factors. In general the reaction is conducted for a period of time which is at least sufiicient to provide the addition or attachment of the active hydrogen from the active hydrogen compound to the isocyanato nitrogen of the novel isocyanate. The remainder of the active hydrogen compound becomes bonded to the carbonyl carbon unless decarboxylation or further reaction occurs. The following equation illustrates the reaction involved.

RN=o=o HZ RNH( JZ wherein H-Z represents the active hydrogen compound. Thus, by way of illustrations the reaction of isocyanato (NCO) with (a) hydroxyl (OH) results in the i -NHC o group; (b) primary amino (NH2) results in the 0 NH( BNH group; (c) secondary amino (NHR) results in the 0 -NHiiNR- group; (d) thiol (SH) results in the group; (e) carboxyl (COOH) can be considered to result in the intermediate 0 0 [NHJJJ O(%] which decarboxylates to the o NHli group; (f) ureylene 0 (NH NH) results in the 0 N ll O=(JNH group (biuret); (g) amido 0 ((L-NHR) results in the C-NONH i I i R group (carbonylurea); (h) urethane o NHii 0-) results in the O=(]JNH- group (allophanate); (i) water (HOH) can be considered to result in the intermediate which decarboxylates to the NH group; and the like. Most desirably, conditions are adjusted so as to achieve a practical and commercially acceptable reaction rate depending, to a significant degree, on the end use application which is contemplated. In many instances, a reaction period of less than a few hours is oftentimes sufficient for the intended use.

The isocyanate-reactive hydrogen reactions, in many instances, are preferably accomplished in the presence of a catalytically significant quantity of one or more of the catalysts illustrated previously. In general, a catalyst concentration in the range of from about 0.001 weight percent, and lower, to about 2 weight percent, and higher, based on the total weight of the reactants, has been observed to be useful.

The concentration of the reactants can be varied over a 'wide range. Thus, for example, one can employ the active hydrogen compound in such relative amounts that there is provided as low as about 0.1 equivalent (group) of active hydrogen, and lower, per equivalent (group) of isocyanato. In general, about 0.2 and oftentimes about 0.25 equivalent of active hydrogen represent more suitable lower limits. The upper limit can be as high as about 7 equivalents of active hydrogen, and higher, per equivalent of isocyanato. However, for many applications, a desirable upper limit is about 3.5 equivalents of active hydrogen per equivalent of isocyanato. When employing bifunctional compounds (those which contain two active hydrogen substituents such as hydroxyl, carboxyl, primary amino, secondary amino, etc.), a suitable concentration would be from about 0.25 to about 3 equivalents of active hydrogen substituent from the bifunctional compound per equivalent of isocyanate. It is readily apparent that depending upon the choice and functionality of the active hydrogen compound(s), the choice of the isocyanate(s), the proportions of the reactants, etc., there can be obtained a myriad of novel compounds and products which range from the liquid state to solids which can be fusible solids, thermoplastic solids, partially cured to essentially completely cured, thermoset solids, etc. Many of the novel liquid to non-crosslinked solid compositions contain a plurality of polymerizable ethylenic bonds which serve as vinyl polymerization sites With vinyl monomers such as those illustrated previously, e.g., styrene, butadiene, vinyl chloride, vinyl acetate, methyl acrylate, etc., under the operative conditions noted supra.

A class of novel compounds, i.e., blocked isocyanates, which deserve special mention are those which contain the O -NHiigrouping therein. Among the compounds which fall into this category are those in which the variable G of Formula I supra is characterized as follows:

wherein R, R R R a, b, n, and m have the meanings (as well as the provisos) set out in Formula I supra; and wherein Z is an abbreviated form for the monofunctional active organic compounds sans the active hydrogen atom. Illustrative Z radicals include those which result from the reaction of, for example, stoichiometric quantities of the novel isocyanates of Formula I supra with monofunctional active organic compounds as illustrated by primary amines, secondary amines, primary alcohols, secondary alcohols, phenols, primary thiols, secondary thiols, imines, amides, ureas, etc. The scope of Z is readily apparent from the description re the active hydrogen compounds as well as from a consideration of Equation II supra. Moreover, by employing, for example, less than stoichiometric quantities of monofunctional active organic compound to novel isocyanate, i.e., less than one equivalent of active hydrogen substituent per equivalent of isocyanate group, there are obtained novel partially blocked isocyanate compounds. These partially blocked compounds will contain both NCO and 0 -NH( i1Z groupings. Preferred compounds include the novel blocked and partially blocked bis(isocyanatoalkyl) 5- norbornene-2,3-dicarboxylates, e.g., bis(2-isocyanatoethyl) 5-norbornene-2,3-dicarboxylates; the hexachlorinated bis(isocyanatoalkyl) 5-norbornene-2,3-dicarboxylates, e.g., bis(2-isocyanatoethyl) 1,4,5,6,7,7 hexachloro-S-norbornene-2,3-dicarboxylate; and the like.

Useful and interesting polymeric products are obtained by the vinyl polymerization of an admixture comprising the polymerizable blocked (and/or the partially blocked) isocyanates of Formula III and an ethylenically unsaturated organic compound.

A particular desirable class of novel polyurethane diols which are contemplated within the scope of the teachings of this specification are those which result from the reaction of a dihydroxy compound such as those illustrated previously, with a molar deficiency, i.e., a stoichiometric deficiency, of the novel diisocyanates which fall within Formula I supra. The highly preferred dihydroxy compounds are the alkylene glycols, the polyether glycols, the polyoxyalkylated diols, the polyester diols, and the initiated lactone polyester diols, especially those dihydroxy compounds which have average molecular weights as low as about 60 and as high as about 7000, and higher. A preferred average molecular weight range is from about 300 to about 5000. The initiated lactone polyester diols which have an average molecular weight of from about 500 to about 4000 are eminently preferred since within this molecular weight range there can be prepared, for example, polyurethane products such as cast resins and thermoplastic products. Equation IV below illustrates the linear extension reaction involved:

1V HAOH deficient Q(NC o);

HO[A0 NHQNH OLAOH ll ll Polyurethane Diol wherein HO-A-OH is an abbreviated representation of the organic dihydroxy compounds, the variable A being an organic divalent aliphatic radical such as those illustrated previously; wherein Q(NCO) is an abbreviated representation for the novel diisocyanates encompassed within the scope of Formula I supra; and wherein n is a number having an average value of at least one.

It will be noted from Equation IV that the degree of linear extension is realistically controlled by the amount of the reactants employed. If the proportions of diol and diisocyanate are chosen so that the number of reactive hydroxyl groups on the diol are equal to the number of reactive isocyanate groups on the diisocyanate, then relatively long, high molecular weight chains can be formed. In general, one can employ such relative amounts so that there is provided slightly greater than one equivalent of hydroxyl group from the diol per equivalent of isocyanato group from the diisocyanate. It is desirable, however, to employ amounts of diol and organic diisocyanate (in Equation IV) so that there is provided a ratio of from about 1.1 to about 2.2 equivalents, and higher, of hydroxyl group per equivalent of isocyanato group, and preferably from about 1.3 to about 2 equivalents of hydroxyl group per equivalent of isocyanato group.

It is to be understood that in lieu of the dihydroxy compounds employed in Equation IV one can employ higher functional polyols such as the triols, tetrols, etc., and obtain novel polyurethane triols, tetrols, etc. In addition, admixtures of dihydroxy compounds, or dihydroxy compounds plus higher functional hydroxy compounds, can be employed.

An eminently preferred class of novel polyurethane diisocyanates which are contemplated are those which result from the reaction of a dihydroxy compound exemplified previously, with a molar excess of the novel diisocyanates of Formula I supra. The highly preferred dihydroxy compounds which can be employed include those illustrated in the discussion to Equation IV supra as Well as the resulting polyurethane diol products (of Equation IV). Equation V below illustrates this linear extension reaction involved:

v HO-A-OH excess QCNCOM 0 0 ll e OCN[QNH 0A0 NH]..QNCO Polyurethane Diisocyanate (Prepolymer) wherein all the variables of Equation V have the meanings set out in Equation IV previously.

It will be noted from Equation V that the use of an excess of diisocyanate provides an eflicient means of control over the degree of linear extension of the polyurethane molecule. If the proportions of diol and diisocyanate are chosen so that the number of reactive terminal hydroxy groups on the diol are equal to the number of reactive isocyanate groups on the diisocyanate as indicated previously, relatively long, high molecular weight chains would be formed. It is desirable, for many applications, to employ amounts of diisocyanate and diol (in Equation V) so that there is provided a ratio of greater than about one equivalent of diisocyanate per equivalent of diol, preferably from about 1.05 to about 7 equivalents, and higher, of diisocyanate per equivalent of diol, and preferably still from about 1.2 to about 4 equivalents of diisocyanate per equivalent of diol.

During and after preparation of the isocyanato-terminated reaction products it is oftentimes desirable to stabilize said reaction products by the addition of retarders to slow down subsequent further polymerization or less desirable side-reactions such as, for example, allophanate formation. Retarders may be added to the diisocyanate, diol, and/or the aforesaid reaction products. Illustrative of the retarders suitable for the diol-diisocyanate reaction are hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, acetyl chloride, para-toluenesulfonyl chloride, phosphorous trichloride, phosphorous oxychloride, sulfuryl chloride, thionyl chloride, and sulfur dioxide.

In lieu of, or in conjunction with the dihydroxy reactants of Equation V, it is oftentimes desirable to empoly higher functional polyols such as the triols, tetrols, etc., and obtain novel polyurethane triisocyanates, tetraisocyanates, etc.

Another particular desirable class of novel compounds which are contemplated are the novel polyurea diamines which are prepared via the reaction of a diamino compound (which contain two groups from the class of primary amino, secondary amino, and mixtures thereof) as illustrated previously with a molar deficiency of the novel diisocyanates. Equation VI below illustrates this linear extension reaction involved:

0 O HN- DN iJ NHQNHiiN DNH 1'. L l. I'LL l Polyurea Dlamine wherein HN-D-NH is an abbreviated representation of a diarnine compound (the R variables representing hydrogen; a monovalent hydrocarbon or azahydrocarbon radical, e.g., alkyl, aryl, aralkyl, azaalkyl, and the like; and D representing a divalent organic radical, e.g., a divalent aliphatic, alicylic, aromatic, or heterocyclic radical), and wherein Q(NCO) and n have the meanings set forth in Equation IV supra. In general, one can employ slightly greater than about one and upwards to about two, and higher, equivalents of amino group per equivalent of isocyanato group. In lieu of, or in conjunction with, the diamino reactants of 'Equation VI, it is oftentimes desirable to employ higher functional polyamines such as the triamines, tetraamines, etc., and obtain novel polyurea triamines, polyurea tetraamines, etc.

On the other hand, the use of a molar excess of diisocyanate with relation to the diamino compound produces novel polyurea diisocyanates as illustrated by Equation VII:

1 O O 0 CN QNH NDNiiNH QNC O L l l. l

Polyurea Diisocyanate In the reaction exemplified by Equation VII supra, there can be employed silghtly greater than about one and upwards to about 3, and higher, equivalents of isocyanato 27 group per equivalent of amino group. Higher functional polyamines can be employed instead of, or admixed with, the diamines, to thus yield novel polyurea triisocyanates, polyurea tetraisocyanates, etc.

If desired, the preceding novel linear extension reactions can be carried out in the presence of essentially inert normally-liquid organic vehicles such as various organic solvents, depending upon the further application which may be intended for said reaction products.

In another aspect, the invention is directed to the preparation of cast polyurethane systems. Highly useful rigid to flexible, polyurethane resins which can range from slightly crosslinke'd products to highly crosslin-ked products can be prepared by the novel polyisocyanates of Formula I supra and/or the polyurethane polyisocyanto reaction products discussed in the section re Equation V with a polyfunctional chain extender whih contains at least two functional groups that are primary amino (NH secondary amino (NHR), hydroxyl (-OH), or mixtures thereof. The polyisocyanate and polyfunctional chain extender are employed in such relative amounts that there is provided at least about one equivalent (group) of isocyanato (NCO) from the polyisocyanate per equivalent (group) of functional group (hydroxyl and/or amino) from the polyfunctional compounds. When employing solely difunctional compounds as the chain extender(s). it is desirable to employ such relative amounts that result in greater than about one equivalent of NCO, e.g., at least about 1.02 equivalents of NCO, from the polyisocyanate per functional group from the difunctional compound. However, it is oftentimes highly satisfactory when employing polyfunctional chain extenders which contain 3 or more functional groups, alone or in admixture with difunctional chain extenders, to employ such relative amounts so that there is provided at least about one equivalent of NCO from the polyisocyanate per equivalent of functional group from the chain extender(s). Cast polyurethane resins having special utility as printing ink rollers, cast solid urethane industrial tires, mechanical goods such as seals, O-rings, gears, etc., ladies shoe heels, and the like, can be prepared from castable formulations which provide from about 1.02 to aobut 1.6 equivalents of NCO from the polyisocyanate per equivalent of functional group from the polyfunctional chain extender. Optimum properties result from the highly preferred castable formulations which provide from about 1.05 to about 1.4 equivalents of NCO per equivalent of functional group.

It is further highly desirable that the aforesaid polyisocyanate be a prepolymer as defined in Equation V supra. It is observed that such prepolymers will yield cast polyurethane resins which vary from exteremely soft flexible products to relatively hard plastic products. Prepolymers which result from the reaction of diisocyanate and the initiated lactone polyester polyols are eminently suitable since cast resins which possess high performance characteristics can be obtained.

Among the polyfunctional chain extenders which can be employed in the castable formulations are those organic compounds exemplified previously which have two or more hydroxyl or amino (primary and secondary) groups including mixtures of such groups such as the polyols, (diols, triols, tetrols, etc.), the polyamines (diamines, triamines, etc.), amino alcohols, and the like. Among the polyfunctional chain extenders which deserve special mention because they result in especially useful cast polyurethane resins of high strength, high tear resistance, relatively low permanent set, good solvent resistance, and/or excellent abrasion resistance can be listed the following: 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, quinitol, 1,4- bis 2-hydroxyethoxy) benzene, 4,4'-bis[ (Z-hydroxyethoxy) phenyl]isopropylidene, trimethylolpropane, triisopropanolamine, ethanolamine, p-aminophenylethyl alcohol, 2,4- and 2,6-toluenediamines, 3,3'-dichloro-4,4diphenylenediamine, and 4,4'-methylene-bis(o-chloroaniline).

28 The preparation of the cast polyurethane products can take place over a wide temperature range, e.g., from about room temperature to about 200 C., and higher. The preferred temperature is in the range of from about 50 C. to

about 150 C. A highly preferred temperature range is from about 60 C. to about 105 C. The upper limit of the reaction temperature, as indicated previously, is realistically controlled by the thermal stability of the reactants and reaction products whereas the lower limit is regulated, to a significant degree, by the reaction rate.

A valuable modification of the cast polyurethane aspect is the use of an admixture containing the polyols exemplified previously with/without the novel polyurethane diols (of Equation IV) plus the novel polyisocyanates (of Formula I) instead of, or in conjunction with, the prepolymer (of Equation V). It is preferred that the previously exemplified polyols be substantially linear hydroxyl-terminated polymers. It is highly preferred that these polymers have an average molecular weight of at least about 60 and upwards to 6000, and higher, and preferably from about 300 to about 5000. The hydroxyl-terminated polymers which are eminently suitable include the alkylene glycols, the polyether glycols, the polyester diols, the polyoxyalkylated diols, and the initiated lactone polyester diols. In this modifiation, the ratios of the equivalents of NCO and the equivalents of functional groups are the same as set forth above. It is understood, of course, that these ratios will include all the NCO groups and all the functional groups in the castable formulation regardless of the source. Thus, for example, if the formulation comprises novel polyurethane diol, novel diisocyanate, and alkanediol, one must take into consideration when computing the equivalents ratio of said formulation, the equivalents of NCO from the diisocyanate with relation to the sum of the equivalents of the hydroxyl groups from the polyurethane diol plus alkanediol.

A further desirable modification of the cast polyurethane aspect is directed to the partial or incomplete reaction of the cast formulation to thus produce a thermoplastic reaction product mass Which contains unreacted or free isocyanato groups. The aforesaid, thermoplastic mass is relatively stable or non-reactive at room temperature, e.g., about 20 C., but possesses the characteristic of being further cured as, for example, by curing same at an elevated temperature for a sufiicient period of time. This curable, isocyanato-containing mass can be prepared by heating the cast formulation or system, e.g., to about C., and higher, and thereafter quenching the resulting partial reaction products (which contain a minor proportion of unreacted isocyanato groups) with an inert fluid in which said reaction products are insoluble, e.g., an inert normally liquid organic non-solvent. The aforesaid curable, isocyanato-eontaining thermoplastic mass can be stored for relatively long periods of time or shipped to customers over great distances without undergoing any appreciable reaction at ambient conditions, e.g.,

about 20 C.

An extremely significant aspect is directed to the preparation of thermoplastic polyurethane resins including curable polyurethane systems. Such useful systems and/or resins can be prepared from formulations (which include the reactants, especially the difunctional reactants, reaction conditions, and modifications thereof) as set out in the preceding aspect (re the cast polyurethanes) with the exception that there is employed at least about one equivalent of functional group, e.g., hydroxyl, primary amino, secondary amino, or mixtures thereof, from the polyfunctional chain extender per equivalent of isocyanato (NCO) from the isocyanate source. In general, a practical upper limit would be about 1.5 equivalents of functional group per equivalent of NCO. Preferred formulations contain from about 1.02 to about 1.3 equivalents of functional group per equivalent of NCO, preferably still from about 1.05 to about 1.15 equivalents of functional group per equivalent of NCO. In other modifica- 29 tions, it is eminently preferred that the thermoplastic formulation contain about One equivalent of functional group per equivalent of isocyanato, especially to prepare thermoplastic elastomers which exhibit high performance characteristics.

The thermoplastic and curable polyurethane resins can be cured or crosslinked with an organic polyisocyanate. In this respect the novel polyisocyanates of Formula I supra, the novel polyisocyanato-containing polymers exemplified previously, and/ or polyisocyanates well known in the literature can be employed, e.g., publication by Siefken [Annalen, 562, pages 122-135 1949)]. Polyisocyanates such as those produced by the phosgenation of the reaction products of aniline and formaldehyde, or p,p,p"- triphenylmethane triisocyanate, represent further illustrations.

In general, the cure can be effected by using an amount of polyisocyanate which is in stoichiometric excess necessary to react with any free or unreacted functional group from the polyfunctional chain extender. In general, from about 1 to about parts by weight of additional polyisocyanate per 100 parts by weight of curable polyurethane resin is adequate to accomplish the cure for most applications. A preferred range is from about 2.5 to about 6 parts by weight of polyisocyanate per 100 parts by weight of curable stock. The additional polyisocyanate can be admixed with the curable polyurethane stock on a conventional rubber mill or in any suitable mixing device and the resulting admixture is cured in the mold at an elevated temperature, e.g., from about 125160 C., in a relatively short period, e.g., a few minutes, or longer. In the mold, the cure is accomplished apparently by a reaction of excess amino or hydroxyl groups with the newly admixed polyisocyanate, and secondly by reaction of the remaining free terminal isocyanato groups with hydrogen atoms of the urea and urethane groups to form a crosslinked resin. By this procedure, there can be obtained cured polyurethane products which range from highly elastomeric materials possessing excellent tensile strength and exceptional low brittle temperature to tough, rigid rubbery materials.

Various modifying agents can be added to the castable or curable formulations among which can be listed fillers such as carbon blacks, various clays, zinc oxide, titanium dioxide, and the like; various dyes; plasticizers such as polyesters which do not contain any reactive end-groups, organic esters of stearic and other fatty acids, metal salts of fatty acids, dioctyl phthalate, tetrabutylthiodisuccinate; glass; asbestos; and the like.

A modification of the thermoplastic and curable polyurethane resins is the preparation of formulations using diisocyanates which are well known in the literature, and subsequently effecting the cure with the novel polyisocyanates of Formula I or V.

A particularly preferred aspect is directed to the preparation of elastomeric and relatively non-elastomeric products, especially elastomeric films and elastic fibers. It has been discovered quite surprisingly, indeed, that there can be prepared excellent elastic polyurethane films and fibers which are derived from substantially linear hydroxyl terminated polymers having an average molecular weight greater than about 500 and the novel diisocyanates, especially the non-halogenated diisocyanates, of Formula I supra. The elastic and relatively non-elastic films and fibers of this aspect are characterized by good resistance to sunlight degradation, good elongation, high resistance to fume aging, i.e., resistance to breakdown caused by nitrous oxide which is commonly found as an impurity in the atmosphere, good tensile and modulus properties, and/or good stability to oxidizing agents such as chlorine bleach.

These novel elastomeric and relatively non-elastomeric films and fibers can be prepared by first reacting the aforesaid substantially linear hydroxyl-terminated polymer with a molar excess of the novel diisocyanate (of Formula I) to produce a substantially linear isocyanatoterminated polyurethane product (known as a prepolymer). The chain extension reaction of said prepolymer with a bifunctional curing compound in accordance with, for instance, well known cast or spinning techniques results in films or fibers as may be the case. In a useful embodiment, the aforesaid substantially linear hydroxylterminated polymers can be linearly extended by reaction with a molar deficiency of an organic diisocyanate to yield substantially linear hydroxyl-terminated polyurethane products which products then can be reacted with a molar excess of the novel diisocyanates to obtain the prepolymer.

The substantially linear hydroxyl-terminated polymer possesses an average molecular weight of at least about 500, more suitably at least about 700, and preferably at least about 1500. The upper average molecular weight can be as high as 5000, and higher, a more suitable upper limit being about 4000. For many of the novel elastic fibers and films which exhibited a myriad of excellent characteristics, the average molecular weight of the starting hydroxyl terminal polymer did not exceed about 3800. In addition, the hydroxyl-terminated polymers possess a hydroxyl number below about 170, for example, from about 20 to about and a melting point below about 70C., and preferably below about 50 C.

Exemplary of the substantially linear hydroxyl-terminated polymers which are contemplated include the alkylene glycols, the polyether glycols, the polyoxyalkylated diols, the polyester diols, and the initiated lactone polyester diols. The initiated lactone polyester diols are eminently preferred since elastomeric films and elastic fibers exhibiting outstanding performance characteristics can be obtained. Of the highly preferred initiated lactone polyester diols are included those which are characterized by at least about 50 mol percent of carbonylpentamethyleneoxy units therein and which possess an average molecular weight of from about 500 to about 5000, particularly from about 600 to about 4000. The remaining portion of the molecule can be comprised of, in addition to the initiator, essentially linear units derived from a cyclic carbonate such as those illustrated previously, e.g., 4,4-dimethyl-2,6-dioxacyclohexanone, 4,4 dicyanomethyl-2,6-dioxacyclohexanone, 4,4-dichloromethyl-2,-dioxacyclohexanone, 4,4 di(methoxymethyl)-2,6-dioxacyclohexanone, and the like; an oxirane compound especially ethylene oxide, 1,2-epoxypropane, the epoxybutanes, etc.; a mono-, di-, and/or trialkyl-epsilon-caprolactone such as the monomethyl-, dimethyl-, trimethyl-, monoethyl-, diethyl-, triethylepsilon-caprolactones, and others exemplified supra; an alpha, alpha-dialkyl-beta-propiolactone such as alpha, alpha-dimethyl-beta-propiolactone; an alpha, alpha-dihaloalkyl-beta-propiolactone as illustrated by alpha, alpha-dichloromethyl-beta-propiolactone; and others. Also highly preferred polymeric diols include the so-called initiated lactone homopolyester diols which are prepared via the reaction of an admixture of epsilon-caprolactone and an initiator which contains two groups from the class of hydroxyl, primary amino, secondary amino, and mixtures thereof, in the presence of a catalyst such as stannous dioctanoate or stannic tetraoctanoate.

Illustrative of the polyether glycols which are contemplated include those illustrated previously as well as those illustrated in column 7, lines 19' through 70 of US. Pat. No. 2,929,804 which patent is incorporated by reference into this disclosure. Many of the polyester diols which are encompassed have been exemplified previously. Others are set forth in columns 4-5 of US. Pat. No. 3,097,192 which patent is incorporated by reference into this disclosure. The initiated lactone polyester diols have been thoroughly illustrated previously; others are disclosed in 31 US. Pat. Nos. 2,878,236, 2,890,208, 2,914,556, and 2,962,524 which patents are incorporated by reference into this disclosure. The polyurethane diols of Equation IV also represent a preferred group of substantially linear hydroxyl-terminated polymers.

The minimization or elimination of crystallinity, if present in the hydroxyl-terminated polymer, can be achieved, as oftentimes is desired, by introducing pendant groups and/or unsymmetrical groups in the polymeric chain as illustrated by lower alkyl groups, e.g., methyl, ethyl, isopropyl, etc.; halo, e.g., chloro, bromo, etc.; ortho-tolylene; and similar groups which do not interfere with the subsequent polymerization under the conditions used. As is readily apparent to those skilled in the art, the choice of the proper reactants will readily yield hydroxylterminated polymers with the desired quantity and type of pendant and/or unsymmetrical groups. Along this vein, polymers of desired molecular weight and melting point can thus be obtained. In addition, the polymer chain can be interrupted with divalent keto, urea, urethane, etc., groups.

The hydroxyl-terminated polymer and diisocyanate can be reacted in such proportions so as to produce either a hydroxyl-terminated polymrethane product or an isocyanato-terminated polyurethane product (prepolymer). A molar ratio of diol to diisocyanate greater than one will yield the hydroxyl-terminated polyurethane whereas a molar ratio less than one will result in the prepolymer.

As indicated previously, in a particularly useful embodiment, there is employed a sufficient molar excess of hydroxyl-terminated polymer, in particular, the initiated lactone polyester diols, with relation to the organic diisocyanate so that there results Substantially linear hydroxyl-terminated polyurethane products which have average molecular weights of from about 1200 to about 5000, and preferably from about 1500 to about 3800.

The hydroxyl-terminated polymers or the abovesaid hydroxyl-terminated polyurethane products then are linearly extended preferably with the non-halogenated diisocyanates of Formula I. This reaction can be carried out by employing a molar ratio of diisocyanate to hydroxyl-terminated compound of from about 1.1:1 to about :1, preferably from about 1.5 :1 to about 3.5 :1, and more preferably from about 2:1 to 2.5 :1.

In the preparation of the hydroxyl-terminated polyurethane products or the prepolymer, the reaction temperature can vary over a broad range such as noted for the isocyanato/ active hydrogen (hydroxyl in this instance) section discussed previously. Of course, the optimum reaction temperature will depend, to a significant degree, upon several variables such as the choice of reactants, the use of a catalyst, the concentration of the reactants, etc. A suitable temperature range is from about 20 C. to about 125 C., and preferably from about 50 C. to about 100 C. The reaction time likewise is largely influenced by the correlation of the variables involved, and can vary from a few minutes to several hours, e.g., from about 0.5 to about 5 hours, and longer. The tertiary amine compounds and/ or the organic metal compounds disclosed in the section which discusses the isocyanato/active hydrogen reactions can be employed as catalysts, if desired. The isocyanato/hydroxyl reactions are suitably carried out in the absence of an inert normally liquid organic vehicle, though one can be employed, if desired.

In the next step, the prepolymer which results from the above discussed isocyanato/hydroxyl reaction is reacted with a bifunctional curing compound which possesses two groups that are reactive with isocyanato groups. Examples of such curing compounds include diamines, diols, amino alcohols, hydrazino compounds, e.g., hydrazine, water, and the like. It is preferred that said curing compound have two reactive groups from the class of alcoholic hydroxyl, primary amino, and second amino. The most preferred reactive group is primary amino. It

is to be understood that primary amino (NH and secondary amino (NHR) include those compounds in which the nitrogen of these amino groups is bonded to a carbon atom as in, for example, ethylenediamine, as well as those compounds in which said nitrogen (of these amino groups) is bonded to another nitrogen atom as in, for instance, hydrazine.

The bifunctional curing compounds have been illustrated previously in the discussion of the active hydrogen compounds. Among the more desirable diamines (which term includes the mono and polyalkylene polyamines which have two and only two primary and/or secondary amino groups) are such compounds as ethylenediamine, 1,2- and 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, the cyclohexylenediamines, the phenylenediamines, the tolylenediamines, 4,4-diaminodiphenylmethane, mand p-xylylenediamine, 3,3 dichloro 4,4 diaminophenylmethane, benzidine, 1,5 diaminonaphthalene, piperazine, 1,4-bis (3-aminopropyl)piperazine, trans 2,5 dimethylpiperazine, and the like.

It is preferred that the diamine contain no groups other than the two reactive amino groups that are reactive with isocyanato. The said diamine can have various substituent groups including chloro, bromo, alkoxy, alkyl, and the like. Generally it is also preferred that the diamine have not more than 15 carbon atoms.

Illustrative of the various diols and amino alcohols include those exemplified previously and, in particular, ethylene glycol, propylene glycol, 2,2 dimethyl 1,3- propanediol, paradibenzyl alcohol, 1,4-butanediol, ethanolamine, isopropanolamine, and the like. Water and hydrazine are also useful bifunctional curing agents. The organic diamines are the preferred curing compounds, with the alkylenediamines being more preferred, and ethylenediamine being most preferred.

The ratio of reactants in the curing step can vary from about 0.8 to about 1.5 equivalents of isocyanato from the prepolymer per equivalent of functional group from the bifunctional curing compound. In many cases, it is desirable to employ approximate stoichiometric proportions of prepolymer and curing compound, i.e., in proportions such that there is present approximately one isocyanato group from the prepolymer per reactive group from the difunctional curing compound. Oftentimes, it is desirable to employ a slight stoiehiometric deficiency or excess of prepolymer, e.g., slightly less than about or slightly greater than about one equivalent (and upwards to about 1.4 equivalents) of isocyanato per equivalent of functional group (from the bifunctional curing compound), and preferably from about one to about 1.2 equivalents of isocyanato per equivalent of functional group.

A preferred method for carrying out the reaction of prepolymer with curing compound is to effect the reaction in an inert normally liquid organic solvent and thus form a solution from which the fibers and films of the invention can be produced by conventional solution spinning and casting techniques. This can be done by dissolving the prepolymer in a solvent to make, for example, from about 5 to about 40 weight percent solid solution (percent based on total solution weight), and then adding the bifunctional curing compound to this solution. The addition will be facilitated if the curing compound is also dissolved in the same solvent. Many solvents can be used for this purpose. The essential requirement is that the solvent be non-reactive with the prepolymer and with the curing compound. Examples of useful solvents include acetone, dimethyl sulfoxide, N,N dimethyformamide, N,N dimethylacetamide, tetrahydrofuran, and the like. N,N-dimethylformamide is a preferred solvent. Acetone alone or in admixture with other organic vehicles such as those illustrated above represent the preferred solvents from commercial and economic standpoints. In this respect, it should be noted that commercial polyurethane fibers prepared from aromatic diisocyanates, e.g., bis(4-isocyanatophenyl)methane (MDI), as far as is known, are not spun 33 or cast from an acetone ssytem. In lieu thereof, a universal solvent utilized in the preparation of the aforesaid commercial polyurethane fibers is the expensive dimethylformamide.

The reaction between the prepolymer and the curing compound can take place readily at room temperature. Therefore, the solution can be spun into a fiber or cast into a film within a relatively short period, e.g., a few minutes, after the curing compound has been added. For example, the solution can usually be cast or spun within minutes after the addition of a diamine to the prepolymer when the reactants are at a temperature of about 25 C. In making fibers, the polymer solution can be wet spun into an aqueous bath, or dry spun, via conventional techniques. Liquids other than water can be employed in the bath, if desired, but water is generally preferred for economic reasons. Ethylene glcol, glycerol, dimethylformamide, and the like, alone or in admixture, with/ without water, are illustrative of such other liquids. The temperature of the bath can be varied over a range of, for instance, 25 C. to 150 C. The fiber is recovered from the bath by conventional techniques, and can be given a post-cure to oftentimes enhance certain of the properties. A cure at elevated temperatures, for example, up to about 125 C., and higher, for periods ranging from several minutes to several hours may be desirable in many instances. For the preparation of fibers, the cure can be conducted for a period, for example, as long as five hours, and longer, whereas the cure can be increased to 16 hours, and longer, for the preparation of films. In any event, the cure, if desired, can be varied in duration to obtain the desired and optimum properties in the final product. Conventional solution casting techniques can be employed in making films.

If gelation should occur during the reaction between the prepolymer and the curing compound in the solvent, it is oftentimes desirable to add a small amount of acid to the prepolymer solution preferably before the curing compound is added. By so doing, the storage life of the solution containing the reaction product of prepolymer and curing compound can be increased significantly, for example, from a storage life in some cases of only a few minutes without the acid to a storage life of up to about several days with the acid. The acid is used in small amounts. For instance, from about 0.005, and lower, weight percent to about 0.6 weight percent of acid, and higher, based on the weight of the prepolymer, has been found to be suitable.

Among the acids and acid-forming compounds which are oftentimes useful for the purpose described in the preceding paragraph can be listed the following: phosphoric acid, phosphorous acid, hydrochloric acid, nitric acid, sulfuric acid, benzoyl chloride, benzene sulfonyl chloride, benzenesulfonic acid, dichloroacetic acid, octylphenyl acid phosphate, stearyl acid phosphate, and boron trifluoride-etherate. It is to be noted that the pKa' of each of the above mentioned acids is less than about 2.5 (The term pKa' refers to the negative of the log of the hydrogen ion ionization constant in aqueous solution). The strong mineral acids which have a pKa' less than about 2.5 represent a preferred subclass. Phosphoric acid is the preferred species.

The characteristics of the novel fibers and films can be varied over a wide range depending, to a significant degree, on the choice and proportion of the hydroxyl terminated polymers (diol), the diisocyanate source, and bifunction-al curing compound, the reaction conditions, etc. The novel fibers and films can range from relatively semielastic to highly elastic. The molecular weights of the resulting novel elastomeric fibers and films are somewhat difiicult to ascertain with exactness. Nevertheless, they are sufiiciently high enough so that significant semi-elastic and elastic properties in the filmand fiber-forming ranges result.

The novel elastic and semi-elastic polymers are highly 34 useful compositions. For instance, in the form of fibers, the polymers can be used to make foundation garments, bathing suits, sporting clothes, elastic waist bands, hose, and the like. In the form of films, the polymers can be employed as elastic sheeting, as rubber bands, and the like.

Another highly significant aspect of the invention is the use of the novel polyisocyanates of Formula I, and/ or the novel prepolymers, and/or the novel polyisocyanato-containing polymers, to prepare foams, e.g., polyurethane foams, which can range from the extremely flexible to the highly rigid state. The prepolymers which are contemplated in this aspect are the polyisocyanatocontaining reaction products which result from the reaction of polyfunctional compounds which contain two or more active hydrogensubstituents as described previously, e.g., diols, triols, tetrols, diamines, triamines, amino alcohols, etc., with the novel polyisocyanates of Formula I. The proportions of the reactants are such that a sulficient stoichiometric excess of diisocyanates with relation to the polyfunctional compound is employed, i.e., the equivalents of -NCO from the diisocyanate with relation to the equivalents of active hydrogen substituent from the polyfunctional compound is greater than one to thus give non-crosslinked polyisocyanato-containing reaction products (containing at least two -NCO groups) which are soluble in various common organic vehicles, e.g., benzene. Eminently desirable, non-yellowing flexible foams can be prepared via the so-called one step method which involves reacting a polyhydroxy compound, preferably one that contains at least three alcoholic hydroxyl groups, with the above-illustrated novel polyisocyanates, especially the novel low molecular weight polymeric aliphatic multiisocyanates, in the presence of a blowing agent such as water, a liquefied gas, and the like. It is desirable to conduct the reaction in the presence of a catalyst and surfactant. The preparation of the flexible foams differs from the preparation of the rigid foams in that it is generally preferred to first prepare What is oftentimes referred to as a quasi prepolymer, and subsequently add thereto the remainder of the polyhydroxy compound, blowing agent, and other ingredients, if employed, e.g., catalyst, surfactant, etc.

As indicated previously, the novel halogenated (especially the hexachlorinated) polyisocyanates can be employed in the preparation of flame-retardant foams, in particular rigid foams. Many of the foams have exhibited the characteristic of charring rather than dripping during the burning test. The novel hexachlorinated polyisocyanates, e.g., bis(2-isocyanatoethyl) 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylate, in admixture with various polyisocyanates especially the monomethyleneand the polymethylene polyphenylene polyisocyanates (which are obtained by the phosgenation of the polyamine reaction products which result from the condensation of aniline with formaldehyde in the presence of a strong acid catalyst, e.g., hydrochloric acid, at elevated temperatures, e.g., 30 C.) represent a particularly preferred aspect of our contribution to the art. The aforesaid monomethyleneand polymethylene polyphenylene polyisocyanates which are eminently qualified are those which are a mixture of the diphenylmethane diisocyanates (MDI with/without the isomers thereof) with various higher polymeric polyisocyanates such as the triand tetraisocyanates. It will be readily appreciated that the composition of the methylene polyphenylene polyisocyanates is determined by the aniline to formaldehyde molar ratios used in the preparation of the polyamine reaction products. The use of an aniline to formaldehyde molar ratios of from about 1.3 to 1.0 to about 2.5 to 1.0 will yield products containing from about 25 to about 70 weight percent of the bis(aminophenyl) methanes, especially MDA, which upon phosgenation will yield the bis(isocyanatophenyl)methanes, especially MDI, in the same weight percent range. Thus, an admixture of the novel halogenated polyisocyanates as illustrated by l-lEDl with the monomethylene and polymethylene polyphenylene polyisocyanates which contain from about 25 to about 70 weight percent of the bis(isocyanatophenyl) methanes, in particular MDI, represent a preferred embodiment in the preparation of flame-retardant foams, especially the rigid type. An admixture which is extremely desirable is one in which the monomethyleneand the polymethylene polyphenylene polyisocyanate portion contains from about to about 60 weight percent of the bis (isocyanatophenyl)methanes such as MDI, possesses average functionalities ranging from about 2.2 to about 3.0, an equivalent weight ranging from approximately 130 to 145, and a viscosity ranging from about 50 to 900 cps. at 25 C. The free NCO content can range from about 30 to about 31.5%. An extremely preferred admixture is one that contains (in addition to the novel halogenated polyisocyanate) a monomethyleneand polymethylene polyphenylene polyisocyanate fraction characterized by a MDI (including isomers thereof, if any) content of approximately to 55 weight percent and an equivalent weight of about 134 to 142. The polyamine reaction products (precursor which is subjected to phosgenation) can be prepared by employing an aniline to formaldehyde molar ratio of about 1.8 $0.2 to 1.0 at a temperature in the range of from about 55 C. to 85 C. using hydrochloric acid as the condensation catalyst. U.S. Pat. No. 2,683,730 describes the preparation of monomethyleneand polymethylene polyphenylene polyisocyanates which contain up to 40 weight percent bis (isocyanatophenyl)methanes. The weight percent of the polyisocyanate admixture can vary over an extremely wide range, e.g., from about 10 to about 90% by Weight of the novel polyisocyanate, based on the total weight of polyisocyanates. It is desirable, however, to employ at least about weight percent of the monomethyleneand polymethylene polyphenylene polyisocyanates, e. g., from about 50 to about 85 weight percent, preferably from about to about 80 weight percent, and up to about 50 weight percent of the novel halogenated polyisocyanates, e.g., from about 15 to about 50 weight percent, preferably from about 20 to about 45 weight percent. Such polyisocyanate admixture when employed as the isocyanate source in the preparation of rigid foams impart eminent characteristics thereto such as fiame-retardancy, charring in lieu of dripping, good mechanical and dimensional stability, K-factor, etc.

A wide scope of polyhydroxy compounds can be employed in the preparation of the novel foams. The preferred polyhydroxy compound are those which contain three or more hydroxy groups. Illustrative polyhdroxy polyhydroxy compounds include the following classes of compounds (as wel las those illustrated previously in this specification) (a) The polyhydroxy initiated lactone polyesters, and the alkylene oxide adducts thereof;

(b) The polyester polyols (including the polyester diols), and the alkylene oxide adducts thereof;

(c) The polyhyroxyalkanes and polyhydroxycycloalkanes, and the alkylene oxide adducts thereof;

(d) the trialkanolamines, and the alkylene oxide adducts thereof;

(e) the polyols derived from polyamines by the addition of alkylene oxide thereto;

(f) the non-reducing sugars and sugar derivatives, and the alkylene oxide adducts thereof;

(g) the alkylene oxide adducts of aromatic amine/ phenol/ aldehyde ternary condensation products;

(h) the alkylene oxide adducts of phosphorus and polyphosphorus acids, and various hydroxyl-terminated phosphites and phosphonates;

(i) the alkylene oxide adducts of polyphenols;

(j) the polytetramethylene glycols;

(k) the functional glycerides, such as castor oil;

(1) The polyhydroxyl-containing vinyl polymers; and the like.

The preferred alkylene oxides" which term will be employed hereinafter include ethylene oxide, 1,2-epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, isobutylene oxide, epichlorohydrin, and mixtures thereof.

Illustrative polyhydroxyalkanes and polyhydroxycycloalkanes include, among others, ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,3-dihydroxybutane, 1,4- dihydroxybutane, 1,4-, and 1,5-, and 1,6-dihydroxyhexane, 1,2-, 1,3-, 1,5-, 1,6- and 1,8-dihydroxyoctane, 1,10- dihydroxydecane, glycerol, 1,2,5-trihydroxybutane, 1,2,6- trihydroxyhexane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane pentaerythritol, xylitol, arabitol, sorbitol, mannitol, and the preferred alkylene oxide adducts thereof.

Examplary trialkanolamines include triethanolamine, triisopropanolamine, and the tributanolamines, and the preferred alkylene oxide adducts thereof.

Among the alkylene oxide adducts of polyamines can be listed the adducts of the preferred alkylene oxide with ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-butanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,2-, 1,3-, 1,4-, 1,5-, and 1,6-hexanediamine, phenylenediamines, toluenediamine, naphthalenediamines, and the like. Illustrative of the resulting adducts which are of particular interest include, N,N,N',N-tetrakis(2 hydroxyethyl)ethylenediarnine, N,N,N',N-tetrakis(2 hydroxypropyl)ethylenediamine, N,N,N,N,N"- pentakis Z-hydroxypropyl diethylenetriamine, phenyldiisopropanolamine, and the like. Others which deserve particular mention are the preferred alkylene adducts of aniline/formaldehyde or substituted-aniline/forrnaldehyde condensation products.

Illustrative of the non-reducing sugars and sugar derivatives contemplated are sucrose; the alkyl glycosides such as methyl glucoside, ethyl glucoside, and the like; the polyol glycosides such as ethylene glycol glucoside, propylene glycol glucoside, glycerol glucoside, 1,2,6-hexanetriol glucoside, and the like; and the preferred alkylene oxide adducts thereof.

Preferred alkylene oxide adducts of polyphenols include those in which the polyphenol can be bisphenol A; bisphenol F; the condensation products of phenol and formaldehyde, more particularly the novolac resins; the condensation products of various phenolic compounds and acrolein, the simplest members of this class being the 1,1,3-tris(hydroxyphenyl)propanes; the condensation products of various phenolic compounds and glyoxal, glutaraldehyde, and other dialdehydes, the simplest members of this class being the l,1,2,2-tetrakis(hydroxyphenyl) ethanes, and the like.

Another suitable class of polyhydroxy compounds include the preferred alkylene oxide adducts of aromatic amine/phenol/aldehyde ternary condensation products. The ternary condensation products are prepared by condensing an aromatic amine, for instance, aniline, toluidine, or the like; a phenol such as phenol, cresol, or the like; and an aldehyde preferably formaldehyde; at elevated temperatures in the range of, for example, from about 60 C. to C. The condensation products are then recovered and reacted with said preferred alkylene oxide, using a basic catalyst (e.g., potassium hydroxide), if desired, to produce the polyols. The propylene oxide and mixed propylene-ethylene oxide adducts of aniline/ phenol/formaldehyde ternary condensation products deserve particular mention.

The preferred alkylene oxide adducts of phosphorus and polyphosphorus acids are another useful class of polyols. Phosphoric acid, phosphorous acid, the polyphosphoric acids such as tripolyphosphoric acid, and the like, are desirable for use in this connection. Also useful are phosphites such as tris-(dipropylene glycol) phosphite and the phosphonates which can be produced therefrom by heating in the presence of, e.g., butyl bromide, as well as the alkylene oxide adducts thereof.

Another useful class of polyols are the polytetramethylene glycols, which are prepared by polymerizing tetrahydrofuran in the presence of an acidic catalyst.

Also useful are castor oil and alkylene oxide adducts of castor oil.

Another useful class of polyols are various polymers that contain pendant hydroxyl groups. Illustrative are polyvinyl alcohol, vinyl chloride-vinyl alcohol copolymers, and other copolymers of variou ethylenically-unsaturated monomers and vinyl alcohol. Also useful are polymers formed by reacting a dihydric phenol [for instance, 2,2-bis(4-hydroxyphenyl)-propane] with epichlorohydrin in the presence of sodium hydroxide, such as the polymers disclosed in US. Pat. No. 2,602,075.

The polyhydroxy compound, including mixtures thereof, employed in the foam formulation can have hydroxyl numbers which vary over a wide range. In general, the hydroxyl numbers of these polyols can range from about 20, and lower, to about 1000, and higher, preferably from about 30 to about 600, and more preferably from about 35 to about 450.

The functionality and the hydroxyl number of the polyhydroxy compound are signillcant factors which enter into consideration in the preparation of foams. Thus, the polyol preferably possesses a hydroxyl number of from about 200 to about 800 when employed in rigid foam formulations, from about 50 to about 250 for semi-flexible foams, and from about 20 to about 70, or more, when employed in flexible foam formulations. Such limits are not intended to be restrictive, but are merely illustrative of the large number of possible combinations.

In general, it is desirable to employ at least about one --NCO equivalent (group) per hydroxyl equivalent (group) in the preparation of the urethane foamed product. As a practical matter, a slight excess of NCO equivalents with relation to the hydroxyl equivalents is oftentimes employed. For optimum properties, those skilled in the art can readily determine the desired concentration of the reactants. Factors which will influence the concentration are the choice and functionality of the reactants, the end product-whether flexible or rigid, the choice of the blowing agent, the use of a catalyst and/ or surfactant, and other considerations.

As indicated previously, various blowing agents such as water and halogenated hydrocarbons can be employed in the preparation of the foams. The preferred blowing agents are water and certain halogen-substituted aliphatic hydrocarbons which have boiling points between about 40 C. and 70 C., and which vaporize at or below the temperature of the foaming mass. Illustrative are, for example, trichloromonofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, dichloromethane, trichloromethane, bromotrifluoromethane, chlorodifluoromethane, chloromethane, l,l-dichloro-l-fluoroethane, 1,1- difluoro 1,2,2-trichloroethane, chloropentafluoroethane, 1 chloro 1 fluoroethane, 1-chloro-2-fluoroethane, 1,1,2 trichloro 1,2,2-trifluoroethane, 1,1,1-trichloro- 2,2,2 trifluoroethane, 2 chloro-l,1,1,2,3,3,4,4,4-nonafiuorobutane, hexafluorocyclobutane, and octafiuorocyclobutane. Other useful blowing agents include low-boiling hydrocarbons such as butane, pentane, hexane, cyclohexane, and the like. Many other compounds easily volatilized by the exotherm of the isocyanato-hydroxyl reaction also can be employed. A further class of blowing agents includes thermally-unstable compounds which liberate gases upon heating, such as N,N'-dimethyl-dinitrosoterephthalamide.

The amount of blowing agent used will vary with the density desired in the foamed product. In general it may be stated that for 100 grams of reaction mixture containing an average isocyanato/reactive hydrogen ratio of about 1.1, about 0.005 to 0.3 mol of gas are used to provide densities ranging from 30 to 1 pounds per cubic foot, respectively.

In producing foamed reaction products, it also within the scope of the invention to employ small amounts, e.g., about 0.001% to 5.0% by weight, based on the total reaction mixture, of an emulsifying agent such as a polysiloxane-polyoxyalkylene block copolymer having from about 10 to percent by weight of siloxane polymers and from to 20 percent by weight of alkylene oxide polymer, such as the block copolymers described in US. Pats. 2,834,748 and 2,917,480. Another useful class of emulsifiers are the non-hydrolyzable polysiloxane-polyoxyalkylene block copolymers, such as those described in US. 2,846,458. This class of compounds differs from the above-mentioned polysiloxane-polyoloxayalkylene block copolymers in that the polysiloxane moiety is bonded to the polyoxyalkylene moiety through direct carbon-to-silicon bonds, rather than through carbon-to-oxygen-to-silicon bonds. These copolymers generally contain from 5 to percent, and preferably from 5 to 50 weight percent, of polysiloxane polymer with the remainder being polyoxyalkylene polymer. The copolymers can be prepared, for example, by heating a mixture of (a) a polysiloxane polymer containing a siliconbonded, halogen-substituted monovalent hydrocarbon group, and (b) an alkali metal salt of a polyoxyalkylene polymer, to a temperature suflicient to cause the polysiloxane polymer and the salt to react to form the block copolymer. Other useful emulsifiers and surfactants include such materials as dimethyl silicon oil, polyethoxylated vegetable oils commercially available as Selectrofoam 6903, Emulphor EL-720, and others. Although the use of an emulsifier is desirable to influence the type of foam structure that is formed, the foam products of the invention can be prepared without emulsifiers in some cases.

The use of catalysts is generally desirable in the preparation of the novel foamed compositions. Among the catalysts which are contemplated include the tertiary amines, the phosphines, the organic metal compounds, and mixtures thereof, discussed supra with regard to the catalysts of the isocyanto/active hydrogen reactions. It is extremely advantageous to employ a combination of the tertiary amine compound and the organic tin compound as catalysts in the foam formulation. The catalyst is used in catalytically significant quantities. For instance, concentrations in the range of from about 0.001 weight percent, and lower, to about 2 weight percent, and higher, based on the total foam ingredients, have been found useful.

The techniques for producing polyurethane foams by the one shot, prepolymer, or semi-prepolymer methods are well known in the art, as in exemplified by the Saunders, et a1. text, cited above.

In some cases it is desirable to add a small quantity, e.g., up to 5 parts per parts by weight of polyol, of a dipolar aprotic solvent such as formamide, N,N-dimethylformamide, or dimethyl sulfoxide to the foaming formulation. This serves to open up the cell structure when there is an undesired tendency to form closed-cell foams.

A further aspect of the invention is directed to the preparation of novel laminates and/or reinforced plastic materials which exhibit outstanding and extraordinary characteristics. The novel laminates and reinforced plastic materials exhibit high impact resistance, superior weathering properties, good dye respectively, etc. Moreover, the novel laminates, in many respects, exhibit superior properties at elevated temperatures than those prepared from conventional polyesters. Though reinforced plastic prepared from such conventional polyesters enjoy commercial success, the use of polyurethane and/ or polyurea systems in the subject field represents relatively new technology that does not appear to have been successfully commercialized to any noticeable extent.

The most common reinforcing material is glass, generally in the form of chopped fibers or as a woven glass cloth. The invention pertains, also to other reinforcing material which are set forth in the well documented polyester laminating art. In general, a glass fiber or mat is placed in the reinforcing formulation explained hereinafter in such a manner to essentially eliminate all trapped gases. The glass mat is often placed layer upon layer whereas the glass fiber can be dispersed in a predetermined set pattern, if desired. The formulation then can be cured in a heated mold, generally at superatmospheric pressure.

The reinforcing formulation can comprise (1) the novel polyisocyanates illustrated and/or discussed in the sections pertaining to Formulas I, III, V, and VII, and (2) a polyfunctional active hydrogen compound (especially those which contain at least two groups from the class of hydroxyl, primary amino, and secondary amino, or mixtures of such groups). When employing a novel polyisocyanate which contains a polymerizable carbon-to-carbon double bond and/or polyfunctional active hydrogen compound which contains a polymerizable carbon-to-carbon double bond, there can be incorporated into the formulation a polymerizable ethylenica-lly unsaturated organic compound, preferably those which are free of reactive hydrogen atoms, e.g., styrene, ethylene, propylene, vinyl chloride, vinyl acetate, acrylonitrile, vinylidene chloride, butadiene, etc., and if desired, a conventional vinyl polymerization catalyst, e.g., the dihydrocarbyl peroxides, the hydrocarbyl hydroperoxides, the peralkanoic acids, and the azo-compounds. The properties of the ingredients are such that the formulation will result in a cross-linked resin under the curing conditions. The conditions and techniques employed in the conventional polyester laminating art are translatable in this respect. The above ingredients as Well as the proportion of the ingredients have been illustrated throughout the specification.

The afore-described novel reinforcing formulation is, of course, useful per se, that is, without the incorporation of the filler such as glass, stone, cork, carbon black, lamp black, sand, titanium dioxide, metal turnings, ceramic, various colored pigments, and a host of other essentially inert material. Curing the reinforcing formulation results in novel urea and/or urethane products. These products (depending upon whether or not and what kind of filler is employed) can be used as sealants, gaskets, O-ring, floor and wall tile, ceramic facing on the exterior of buildings, etc. They can be machined, molded, extruded, fabricated, etc., into various shapes depending upon the type of ingredients employed. The curing of the novel reinforcing formulation can be conducted over a wide temperature range by employing the operative conditions noted in the discussion re the active hydrogen section supra. The ratio of the NCO/active hydrogen can be varied as discussed previously in the NCO/active hydrogen section.

Another aspect of the invention is directed to the preparation of novel adhesive formulations which exhibit superior bond strength, no discernible creeping, etc. These adhesive formulations can be used to bond metal to metal surfaces, fiber to rubber surfaces (such as in tire cords), cellulosic (such as wood) to cellulosic surfaces, cellulosic to metal surfaces, cellulosic to rubber surfaces, and others.

In general, it should be noted that practically all of the novel aspects or embodiments described herein can be employed as adhesives when properly applied. The application of adhesive formulations is adequately covered in the literature; however, illustrative general procedures are as follows: l) A solution comprising the novel polyisocyanate with/ without rubber in an inert normally-liquid organic vehicle is coated on the metal, fabric, wood, etc. surface. Curing is then effected at room temperature. (2) A solution comprising the prepolymers, polyisocyanato polymeric products, etc. in an inert normally-liquid organic vehicle is applied to the surface to be bonded and then exposed to air for several minutes, e.g., to minutes. The vehicle thus evaporates and moisture from the air initiates the cure. The surfaces then are joined under moderate pressure and cured at room tempertaure or temperatures up to 200 C. (3) A solution comprising the products illustrated by Formulas V to VII contained in an inert normally liquid organic vehicle are supplied to the surface(s) to be bonded. The solvent is allowed to evaporate to form a slight tacky surface. Thereafter the cure is effected under pressure and/or elevated temperatures.

Extremely useful aspects of the invention are directed to the preparation of novel coatings. Such coatings include the one package moisture cure, the two package heat cure, the blocked isocyanates, and isocyanate modified drying oils.

In the one package moisture cure, there is dissolved in an inert normally-liquid organic vehicle a novel polyisocyanate such as illustrated by Formulas I, V, and VII. The resulting solution then is painted on the substrate to be coated. Curing is effected by reaction of the isocyanate group with moisture from the air to form urea linkages. The carbon dioxide which is formed is diffused through the thin coating. The coating can be either tightly or loosely cross-linked, depending on the mechanical properties desired. The quantity of polyisocyanate in the vehicle is readily controlled by the formulator. A prepolymer system is preferred.

In the two-package heat cure, the novel polyisocyanates described throughout this specification are reacted, either in an inert normally-liquid organic vehicle or neat, with a polyfunctional compound which preferably contains hydroxyl, primary amino, and/or secondary amino groups. The polyfunctional compounds which contain at least two hydroxyl groups are preferred. Such compounds encompass, for example, the polyols exemplified previously including the initiated lactone polyester polyols, the polyester polyols, the polyoxyalkylated polyols, the polyether polyols, the alkylene polyols, castor oil, etc. The ratio of NCO/ active hydrogen is generally about one, although it can be greater than or less than one, e.g., about 0.8, and lower, to about 1.2, and higher. When the NCO/ active hydrogen ratio is greater than one, the excess NCO reacts especially at elevated temperatures, or in the presence of a catalyst such as dibutyltin dilaurate, with the urethane or urea groups in the molecule to form allophanate or biuret groups respectively. The characteristics of the ultimate coating or film depend, to a significant degree, on (1) the ratio of NCO/ OH, (2) the cure temperature, (3) the use of catalysts, if any, (4) the characteristics of the polyisocyanate source and the polyfunctional compound, e.g., molecular weight, functionality, etc., (5) the quantity of urethane and urea groups in the polymer chain as well as the distribution of said groups, and the like.

The two package heat cure systems get their name from the obvious fact that the art employs two packages. Thus, one package can comprise the polyisocyanate source, such as the novel prepolymers, generally contained in an inert normally liquid organic vehicle, whereas the second package can contain, for example, the polyol source in the inert vehicle. Either package could contain other ingredients such as catalyst, etc. Any of the novel polyisocyanates described previously can be employed in the two package coating systems. The polyfunctional compounds, especially the preferred polyhydroxy compounds, have been adequately illustrated supra. In addition, ethylenically unsau-trated organic compounds can be employed when the polyisocyanate and/or the polyfunctional compound contain a polymerizable double bond. In such cases, the vinyl polymerization can be effected during the isocyanato/ active hydrogen reaction or cure. Alternatively, the vinyl polymerization can be conducted first, followed by reacting the resultant poly(vinyl isocyanate) with the polyfunctional compounds. Of course, typical vinyl polymerization catalysts are employed if desired.

In the so-called blocked isocyanaite systems, a blocked isocyanate" as illustrated in the discussion re 

